Fatty acids, soaps, surfactant systems, and consumer products based thereon

ABSTRACT

Novel fatty acids and derivatives thereof such as salts, new surfactant systems comprising one or more of these compounds, consumer products such as laundry products, personal care products, pharmaceutical compositions, industrial cleaners, and the like comprising said compounds or surfactant systems.

CROSS REFERENCE

This is a divisional of U.S. application Ser. No. 09/507,823 now U.S.Pat. No. 6,395,701 filed on Feb. 22, 2000, which is continuation under35 USC §120 of PCT International Application Ser. No. PCT/US98/22054,filed Oct. 19, 1998; which claims priority to Provisional ApplicationSer. No. 60/063,603, filed Oct. 23, 1997.

FIELD OF THE INVENTION

The present invention relates to certain novel fatty acids andderivatives thereof such as salts, to new surfactant systems comprisingone or more of these compounds, and to consumer products such as laundryproducts, personal care products, pharmaceutical compositions,industrial cleaners, and the like comprising said compounds orsurfactant systems.

BACKGROUND OF THE INVENTION

Fatty acids and soaps have a long history tracing into antiquity. Theart was highly advanced at the turn of the last century (See, forexample, “Modern Soaps, Candles and Glycerin”, L. L. Lamborn, VanNostrand, New York, 1906). Weighty tomes such as “Industrial Oil and FatProducts”, A. E. Bailey, Interscience, New York, 1951 and “Fatty Acids”,Ed. Klare S. Markley, Parts 1-5, Interscience, N.Y., 1960-1968 provide asystematic entry-point to the art. “Fatty Acids”, Ed. E. H. Pryde,American Oil Chemists' Society, 1979, discusses fatty acids includingsome mention of branched types. Structures, separations and synthesis offatty acids, including some branched examples, are laid out by F. D.Gunstone in “An Introduction to the Chemistry and Biochemistry of FattyAcids and their Glycerides”, Chapman and Hall, London, 1958. Substantialcontributions to methods of synthesis of branched fatty acids were madeby James Cason; see, for example, J. Amer. Chem. Soc., Vol. 66, (1944),p. 46. Certain branched mixed fatty acids with high levels of impuritieswere known in wartime Germany, and have several disadvantages. SeeBailey cited supra at pages 504-506.

Fatty acids, including branched types, can be isolated from naturallyoccurring materials such as vegetable, animal, fish, bird or insect oilsor bacteria and can be isolated from human skin lipids. Likewise theycan be made from petrochemical starting-materials.

Naturally occurring complex mixtures of esters which in principle can behydrolyzed to fatty acid mixtures for example include those disclosed byJuarez et al, Archives of Biochemistry and Biophysics, Vol. 293, pp.331-341 (1992); by Nicolaides et al in Biomedical Mass Spectrometry,Vol. 4., pp. 337-47 (1977); and by Ratnayake et al in Lipids, Vol. 24,pp 630-637 (1989). See also Nicolaides et al., Lipids, Vol. 6., pp.901-905 (1971). Though such disclosures typically identify numerousmonomethyl or polymethyl branched fatty acid derivatives as beingpresent in natural systems, useful amounts of individual compounds aretypically not secured.

Fatty acids and their derivatives, including certain branched types,have an enormous utility to man and have been used in applicationsranging from laundry cleaning agents to anticonvulsive drugs, dermallotions and cosmetics. See, for example, commonly assigned WO 94/12608published Jun. 9, 1994. Such derivatives can have limitations, forexample off-odors; further, it has not always been recognized whichstructures (e.g., primary or secondary carboxyl) are of greatestutility. Some branched fatty acids, more particularly, have been shownto have unusual properties, such as low melting points relative to equalcarbon number linear analogs. In view of the age and extent of the art,improvements are becoming more difficult to achieve and what at firstmay appear to be small advances may carry great weight.

Commercially described branched fatty acids of varying availabilityinclude a few from Exxon, Shell, Henkel, Sasol and others; see thetechnical publications of these suppliers. Many of such materialscontain quaternary carbon atoms. Perhaps the most common branched fattyacid type useful as a surfactant but too costly and limited inavailability for high-volume applications and moreover, lacking informulation flexibility, is isostearic acid; there are also someshort-chain types, for example 2-ethylhexanoic acid, but these arerelatively unuseful as surface-active agents. In short, there is asevere limitation in flexibility to the formulator when this handful ofcurrently commercial types of branched fatty acid or mixture is reliedon.

There is therefore an ongoing need for improvement in the field ofbranched fatty acid compositions. Accordingly, it is an object herein toprovide such improvements, particularly novel fatty acids, soaps andderivatives, especially those capable of improving one or more of thefollowing technological systems: surfactants and surfactant systems;cosurfactants; builders; antifoams; emollients and skin feel agents;particularly important is to accomplish improvements useful for theformulator of consumer products such as personal care products andlaundry and cleaning products.

BACKGROUND ART

As noted, certain branched-chain fatty acids have been known for sometime in the art. See, for example, “Fatty Acids (Branched-Chain)” inKirk-Othmer's Encyclopedia of Chemical Technology, 1st. Edition, (1951),Interscience Publishers, Vol. 6, at pages 262-266, WO9807680, WO9807679and references cited therein including, for example, several papers byCason et al.

Known branched-chain fatty acids (for example those recognized byChemical Abstracts by Registry numbers or those which can be found bymanual searching of the older Chemical Abstracts) are nonlimitinglyillustrated by: 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-methyldecanoic acid;2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- and 10-methylundecanoic acid; 2-, 3-, 4-,5-, 6-, 7-, 8-, 9-, 10- and 11-methyldodecanoic acid; 2-, 3-, 4-, 5-,8-, 9-, 11- and 12-methyltridecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-,9-, 10-, 11-, 12-, and 13-metbyltetradecanoic acid; 2-, 3-, 4-, 6-, 7-,10-, 11-, 12-, 13- and 14-methylpentadecanoic acid; 2-, 3-, 4-, 5-, 6-,7-, 8-, 9-, 10-, 11-, 12-, 13-, 14- and 15-methylhexadecanoic acid; 2-,3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15- and16-methylheptadecanoic acid; 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12-, 13-, 14-, 15-, 16- and 17-methyloctadecanoic acid; 2-, 3-, 4-, 10-,17- and 18-methylnonadecanoic acid.

In particular with respect to the above compounds,11-methylpentadecanoic acid, 8-methyloctadecanoic acid and14-methyloctadecanoic acid have been disclosed in U.S. Pat. No.4,997,456 and commonly assigned U.S. Pat. Nos. 4,000,340 and 4,076,633disclose 15-methyloctadecanoic acid.

Also known in the art and identified by Chemical Abstracts throughregistry numbers or locatable in early Chemical Abstracts are: 2,2-,2,3-,and 2,4-dimethyldecanoic acid; 2,2-, 2,3-, 2,4-, 2,6- and2,8-dimethylundecanoic acid; 2,2-, 2,3-, 2,4-, 2,6-, 2,8- and2,10-dimethyldodecanoic acid; 2,4-, 2,5-, 2,6-, 2,8- and2,10-dimethyltridecanoic acid; 2,2-, 2,3-, 2,4-, 2,6-, 2,8-, and2,10-dimethyltetradecanoic acid, 2,4-, 2,6-, 2,10-, 2,12- anddimethylpentadecanoic acid; 2,2-, 2,4-, 2,6-, 2,10-, 2,12- and2,14-dimethylhexadecanoic acid; 2,2-, 2,4-, 2,5-, 2,6- and2,10-dimethylheptadecanoic acid; 2,2-, 2,3-, 2,4- and2,9-dimethyloctadecanoic acid; and 2,2-dimethylnonadecanoic acid.

Also known in the art and identified by Chemical Abstracts throughregistry numbers or locatable in early Chemical Abstracts are: 3,3-,4,4- and 5,9-dimethyldecanoic acid; 3,3-, 3,5-, 3,7-, 3,9-, 4,8-, 9,9-and 10,10-dimethylundecanoic acid; 3,3-, 3,5-, 3,7-, 3,9-, 3,11-, 4,8-and 4,10-dimethyldodecanoic acid; 3,3-, 3,4-, 3,5-, 3,7-, 3,9-, 3,11-,4,8-, 5,7-, 10,10-and 12,12-dimethyltridecanoic acid; 3,3-, 3,5-, 3,7-,3,9-, 3,11-, 4,4-, 4,8-, 5,7-, 5,9-, 6,10-, 7,8-, 6,12-, 6,13-, 8,8-,9,13- and 10,13-dimethyltetradecanoic acid; 3,3-, 3,5-, 3,6-, 3,7-,3,9-, 3,11-, 3,13-, 4,8-, 4,10-, 5,9-, 6,8-, 6,10-and14,14-dimethylpentadecanoic acid; 3,3-, 3,7-, 4,8-, 4,10-, 4,14-, 5,9-,6,12-, 7,9-, 8,12-, 8,14-, 11,15- and 15,15-dimethylhexadecanoic acid;3,3-, 5,9-, 8,10- and 12,16-dimethylheptadecanoic acid; 3,3-, 7,9-,9,10-, 9,11- and 17,17-dimethyloctadecanoic acid; and3,3-dimethylnonadecanoic acid. In a few cases, the acids must beextracted from natural mixtures of fatty esters.

As referred to in Kirk Othmer's article supra, other branched fattyacids known in the literature include: 2,9-dimethyloctadecanoic acid,14-ethylhexadecanoic acid, 15-ethylheptadecanoic acid, and12-n-hexyloctadecanoic acid. There are also numerous known examples ofbranched fatty acids containing quaternary carbon atoms, for example,any of the known 2,2-dimethyl substituted long-chain fatty acidsspecifically named hereinabove.

The known trimethyl-substituted fatty acids, having chemical abstractsregistry numbers, include: 2,5,9-trimethyldecanoic acid; 2,4,5-, 2,4,6-and 2,6,10-trimethylundecanoic acid; 2,4,6-, 2,4,8-, 2,6,10- and3,7,11-trimethyldodecanoic acid; 4,8,12-, 3,7,9-, 3,5,9-, 2,4,10-,2,4,8-, 2,4,6-, 2,6,10- and 4,8,12-trimethyltridecanoic acid; 2,4,6-,2,4,8-, 2,6,10-, 3,6,13-, 3,7,9-, 3,7,11- and5,9,13-trimethyltetradecanoic acid; 2,4,6-, 2,4,8-, 3,4,7-, 3,5,9-,3,7,9-, 3,7,11-, 3,9,11-, 3,14,14- and 6,10,14-trimethylpentadecanoicacid; 2,3,4- and 2,4,8-trimethylhexadecanoic acid;4,8,12-trimethylheptadecanoic acid; 2,4,8-trimethyloctadecanoic acid;and 4,8,12-trimethyloctadecanoic acid.

The known polymethyl-substituted fatty acids include:2,4,6,8-tetramethylundecanoic acid; 2,4,6,8,10-pentamethyldodecanoicacid; 3,7,9,11- and 3,5,9,11-tetramethyltridecanoic acid;2,2,4,6,8,10-hexamethyltridecanoic acid; 3,9,11,13-, 3,7,11,13-,3,7,9,11-, 2,4,6,10-, 3,5,11,13-, 3,5,9,11-, 2,4,8,10- and3,3,12,12-tetramethyltetradecanoic acid;2,6,10,14-tetramethylpentadecanoic acid; 2,6,10,14- and3,7,11,15-tetramethylhexadecanoic acid;4,8,12,16-tetramethylheptadecanoic acid;5,7,13,17-tetramethyloctadecanoic acid; and2,2,17,17-tetramethyloctadecanoic acid.

Known monoethyl-substituted fatty acids include: 2-, 4- and6-ethyldecanoic acid; 2-ethylundecanoic acid; 2-, 4-, 6- and10-ethyldodecanoic acid; 2-ethyltridecanoic acid; 2-, 4- and6-ethyltetradecanoic acid; 4- and 13-ethylpentadecanoic acid;2-ethylhexadecanoic acid; 2- and 15-ethylheptadecanoic acid; 2-, 3-, 9-,12- and 16-ethyloctadecanoic acid; and 2-ethylnonadecanoic acid.

Known monopropyl-substituted fatty acids include: 2-propyldecanoic acid,2- and 3-propylundecanoic acid; 2- and 6-propyldodecanoic acid;2-propyltridecanoic acid; 2- and 3-propyltetradecanoic acid; 2- and3-propylpentadecanoic acid; 2-, 3- and 4-propylhexadecanoic acid;2-propylheptadecanoic acid; and 2-propyloctadecanoic acid.

Other known substituted fatty acids include 2-ethyl-6-ethyl, 2,2-diethyland 2-ethyl-6-methyldecanoic acid; 2-ethyl-6,8-dimethyl,2-ethyl-4,6-dimethyl and 2-ethyl-6-methylundecanoic acid;2-ethyl-4,6,10-trimethyl, 2-ethyl-6,10-dimethyl, 2-ethyl-6,8-dimethyl,2-ethyl-4,6-dimethyl and 2-ethyl-6-methyldodecanoic acid;2,8-diethyl-12-methyl, 2-ethyl-12-methyl and2-ethyl-10-methyltridecanoic acid; 2,10-diethyl-6-methyl,2-ethyl-6,10-dimethyl, 2-ethyl-6,8-dimethyl, and2-ethyl-4,8-dimethyltetradecanoic acid.

Yet other substituted fatty acids known in the art include: 2,2-diethyland 6-ethyl-2,4-dimethyldecanoic acid; 4-ethyl-5-methyl and3-ethyl-3-methylundecanoic acid; 2,2-diethyldodecanoic acid;3-ethyl-3-methyltridecanoic acid; 3-ethyl-3-methylpentadecanoic acid;4,6-diethylhexadecanoic acid; 4,6-diethyl and2-ethyl-2-propyloctadecanoic acid; and 3-ethyl-3-methylnonadecanoicacid.

In referring especially to the early literature, the following termshave been used as synonyms:

decanoic acid: capric acid

undecanoic acid: undecylic acid or hendecanoic acid

dodecanoic acid: lauric acid

tridecanoic acid: tridecoic acid

tetradecanoic acid: myristic acid

pentadecanoic acid: no early synonym

hexadecanoic acid: palmitic acid

heptadecanoic acid: margaric acid

octadecanoic acid: stearic acid

nonadecanoic acid: nonadecoic acid

Additionally, with respect to substitution positions in fatty acids, thefollowing greek letters used in the past are synonymous to the indicatednumbered positions of substitution:

α=2, β=3, γ=4, δ=5, ε=6, ζ=7, η=8, θ=9, ι=10, κ=11, λ=12, μ=13, ν=14,ξ=15, ο=16, π=17, ρ=18, σ=19.

Thus, for example, the modem term “2,2-dimethylheptadecanoic acid” andthe older term α,α-dimethylmargaric acid” are perfectly synonymous.

SUMMARY OF THE INVENTION

The present invention encompasses improvements in consumer products,especially laundry detergents and cleaning products, made possiblethough innovation in fatty acids and their derivatives. Consumerproducts ranging from personal care products to cosmetics and paperproducts, into which the materials can be formulated, are encompassed.

More particularly, in one aspect, the invention encompasses acomposition of matter comprising the acid, lower alkyl esters,stereoisomers, or salts of at least one branched carboxylic acidselected from the group consisting of:

(a) 5-, 6-, 7-, 8-, 9-, 12-, 13-, 14-, 15- and 16-methylnonadecanoicacid; 6-, and 7-methyltridecanoic acid; 5-, 8- and 9-methylpentadecanoicacid; and mixtures thereof;

(b) 2,5-, 2,7-, and 2,9-dimethyldecanoic acid; 2,5-, 2,7-, 2,9-, and2,10-dimethylundecanoic acid; 2,5-, 2,7-, 2,9- and2,11-dimethyldodecanoic acid; 2,3-, 2,7-, 2,9-, 2,11- and2,12-dimethyltridecanoic acid; 2,5-, 2,7-, 2,9-, 2,11-, 2,12- and2,13-dimethyltetradecanoic acid; 2,3-, 2,5-, 2,7-, 2,8-, 2,9-, 2,11- and2,13-dimethylpentadecanoic acid; 2,3-, 2,5-, 2,7-, 2,8-, 2,9-, 2,11-,2,13- and 2,15-dimethylhexadecanoic acid; 2,3-, 2,7-, 2,8-, 2,9-, 2,11-,2,12-, 2,13-, 2,14-, 2,15- and 2,16-dimethylheptadecanoic acid; 2,5-,2,6-, 2,7-, 2,8-, 2,10-, 2,11-, 2,12-, 2,13-, 2,14-, 2,15-, 2,16- and2,17-dimethyloctadecanoic acid; and mixtures thereof;

(c) 3,4-, 3,5-, 3,6-, 3,8-, 3,9-, 4,5-, 4,7-, 4,9-, 5,6-, 5,7-, 5,8-,6,7-, 6,8-, 6,9-, 7,8-, 7,9- and 8,9-, dimethyldecanoic acid; 3,4-,3,6-, 3,8-, 3,10-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 5,6-, 5,7-, 5,8-,5,9-, 5,10-, 6,7-, 6,8-, 6,9-, 6,10-, 7,8-, 7,9-, 7,10-, 8,9-, 8,10- and9,10-, dimethylundecanoic acid; 3,4-, 3,6-, 3,8-, 3,10-, 4,5-, 4,6-,4,7-, 4,9-, 4,11-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-, 6,7-, 6,8-,6,9-, 6,10-, 6,11-, 7,8-, 7,9-, 7,10-, 7,11-, 8,9-, 8,10-, 8,11-, 9,10-,9,11-, and 10,11-dimethyldodecanoic acid; 3,6-, 3,8-, 3,10-, 3,12-,4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 5,6-, 5,8-, 5,9-, 5,10-,5,11-, 5,12-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 7,8-, 7,9-, 7,10-,7,11-, 7,12-, 8,9-, 8,10-, 8,11-, 8,12-, 9,10-, 9,12-, 10,11-, 10,12-and 11,12-dimethyltridecanoic acid; 3,4-, 3,6-, 3,8-, 3,10-, 3,12-,3,13-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 5,6-, 5,8-,5,10-, 5,11-, 5,12-, 5,13-, 6,7-, 6,8-, 6,9-, 6,11-, 7,9-, 7,10-, 7,11-,7,12-, 7,13-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 9,10-, 9,11-, 9,12-,10,11-, 10,12-, 11,12-, 11,13- and 12,13-, dimethyltetradecanoic acid;3,4-, 3,8-, 3,10-, 3,12-, 3,14-, 4,5-, 4,6-, 4,7-, 4,9-, 4,11-, 4,12-,4,13-, 4,14-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 6,7-,6,9-, 6,11-, 6,12-, 6,13-, 6,14-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-,7,13-, 7,14-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 8,14-, 9,10-, 9,11-,9,12-, 9,13-, 9,14-, 10,11-, 10,12-, 10,13-, 10,14-, 11,12-, 11,13-,11,14-, 12,13-, 12,14- and 13,14-, dimethylpentadecanoic acid; 3,4-,3,5-, 3,6-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 3,15-, 4,5-,4,6-, 4,7-, 4,9-, 4,11-, 4,12-, 4,13-, 4,15-, 5,6-, 5,7-, 5,8-, 5,10-,5,11-, 5,12-, 5,13-, 5,14-, 5,15-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-,6,13-, 6,14-, 6,15-, 7,8-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-, 7,15-,8,9-, 8,10-, 8,11-, 8,13-, 8,15-, 9,10-, 9,11-, 9,12-, 9,13-, 9,14-,9,15-, 10,11-, 10,12-, 10,13-, 10,14-, 10,15-, 11,12-, 11,13-, 11,14-,12,13-, 12,14-, 12,15-, 13,14-, 13,15- and 14,15-, dimethylhexadecanoicacid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 3,13-,3,14-, 3,15-, 3,16-, 4,5-, 4,6-, 4,7-, 4,8-, 4,9-, 4,10-, 4,11-, 4,12-,4,13-, 4,14-, 4,15-, 4,16-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-, 5,12-,5,13-, 5,14-, 5,15-, 5,16-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-,6,13-, 6,14-, 6,15-, 6,16-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-,7,14-, 7,15-, 7,16-, 8,9-, 8,11-, 8,12-, 8,13-, 8,14-, 8,15-, 8,16-,9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 9,15-, 9,16-, 10,11-, 10,12-, 10,13-,10,14-, 10,15-, 10,16-, 11,12-, 11,13-, 11,14-, 11,15-, 11,16-, 12,13-,12,14-, 12,15-, 13,14-, 13,15-, 13,16-, 14,15-, 14,16- and 15,16-,dimethylheptadecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-,3,11-, 3,12-, 3,13-, 3,14-, 3,15-, 3,16-, 3,17-, 4,5-, 4,6-, 4,7-, 4,8-,4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 4,15-, 4,16-, 4,17-, 5,6-,5,7-, 5,8-, 5,9-, 5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 5,15-, 5,16-,5,17-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 6,13-, 6,14-, 6,15-,6,16-, 6,17-, 7,8-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-, 7,15-, 7,16-,7,17-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 8,14-, 8,15-, 8,16-, 8,17-,9,12-, 9,13-, 9,14-, 9,15-, 9,16-, 9,17-, 10,11-, 10,12-, 10,13-,10,14-, 10,15-, 10,16-, 10,17-, 11,12-, 11,13-, 11,14-, 11,15-, 11,16-,11,17-, 12,13-, 12,14-, 12,15-, 12,16-, 12,17-, 13,14-, 13,15-, 13,16-,13,17-, 14,15-, 14,16-, 14,17-, 15,16-, 15,17- and16,17-dimethyloctadecanoic acid; and mixtures thereof;

(d) 3-, 4-, 5-, 6-, 7- and 8-methyl-2-ethylnonanoic acid; 3-, 4-, 5-,7-, 8-, and 9-methyl-2-ethyldecanoic acid; 3-, 4-, 5-, 7-, 8-, 9- and10-methyl-2-ethylundecanoic acid; 3-, 4-, 5-, 7-, 8-, 9-, 10- and 11-,methyl-2-ethyldodecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9- and11-methyl-2-ethyltridecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12- and 13-methyl-2-ethyltetradecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12-, 13- and 14-methyl-2-ethylpentadecanoic acid; 3-, 4-, 5-,6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14- and15-methyl-2-ethylhexadecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13-, 14-, 15- and 16-methyl-2-ethylheptadecanoic acid; andmixtures thereof;

(e) 3-, 5-, 7- and 8-ethyldecanoic acid; 3-, 4-, 5-, 6-, 7-, 8- and9-ethylundecanoic acid; 3-, 5-, 7-, 8- and 9-ethyldodecanoic acid; 3-,4-, 5-, 6-, 7-, 8-, 9-, 10- and 11-ethyltridecanoic acid; 3-, 5-, 7-,8-, 9-, 10-, 11- and 12-ethyltetradecanoic acid; 3-, 5-, 6-, 7-, 8-, 9-,10-, 11- and 12-ethylpentadecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12- and 13-ethylhexadecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-,10-, 11-, 12-, 13- and 14-ethylheptadecanoic acid; 4-, 5-, 6-, 7-, 8-,10-, 11-, 13-, 14- and 15-ethyloctadecanoic acid; and mixtures thereof;

(f) 3-, 4-, 5-, 6- and 7-propyldecanoic acid; 4-, 5-, 6-, 7- and8-propylundecanoic acid; 3-, 4-, 5-, 7-, 8- and 9-propyldodecanoic acid;3-, 4-, 5-, 6-, 7-, 8-, 9- and 10-propyltridecanoic acid; 4-, 5-, 6-,7-, 8-, 9-, 10- and 11-propyltetradecanoic acid; 4-, 5-, 6-, 7-, 8-, 9-,10-, 11- and 12-propylpentadecanoic acid; 5-, 6-, 7-, 8-, 9-, 10-, 11-,12- and 13-propyihexadecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13- and 14-propylheptadecanoic acid; and mixtures thereof;

(g) 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 4,6-, 4,7-, 5,6-, 5,7- and6,7-dimethyl-2-ethyloctanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-,4,6-, 4,7-, 4,8-, 5,6-, 5,7-, 5,8-, 6,7-, 6,8- and 7,8-,dimethyl-2-ethylnonanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 4,5-,4,6-, 4,7-, 4,8-, 4,9-, 5,6-, 5,7-, 5,8-, 5,9-, 6,7-, 6,8-, 6,9-, 7,8-,7,9- and 8,9-dimethyl-2-ethyldecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-,3,8-, 3,9-, 3,10-, 4,5-, 4,7-, 4,8-, 4,9-, 4,10-, 5,6-, 5,7-, 5,8-,5,9-, 5,10-, 6,7-, 6,9-, 6,10-, 7,8-, 7,9-, 7,10-, 8,9-, 8,10- and9,10-, dimethyl-2-ethylundecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 4,5-, 4,7-, 4,8-, 4,9-, 4,10-, 4,11-, 5,6-, 5,7-,5,8-, 5,9-, 5,10-, 5,11-, 6,7-, 6,9-, 6,11-, 7,8-, 7,9-, 7,10-, 7,11-,8,9-, 8,10-, 8,11-, 9,10-, 9,11- and 10,11-dimethyl-2-ethyldodecanoicacid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 4,5-,4,6-, 4,7-, 4,8-, 4,9-, 4,10-, 4,11-, 4,12-, 5,6-, 5,7-, 5,8-, 5,9-,5,10-, 5,11-, 5,12-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 7,8-, 7,9-,7,10-, 7,11-, 7,12-, 8,9-, 8,10-, 8,11-, 8,12-, 9,10-, 9,11-, 9,12-,10,11-, 10,12- and 11,12-dimethyl-2-ethyltridecanoic acid; 3,4-, 3,5-,3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 4,5-, 4,6-, 4,7-,4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-,5,12-, 5,13-, 6,7-, 6,9-, 6,11-, 6,12-, 6,13-, 7,8-, 7,9-, 7,10-, 7,11-,7,12-, 7,13-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 9,10-, 9,11-, 9,12-,9,13-, 10,11-, 10,12-, 10,13-, 11,12-, 11,13- and12,13-dimethyl-2-ethyltetradecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 4,5-, 4,6-, 4,7-, 4,8-, 4,9-,4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-,5,12-, 5,13-, 5,14-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 6,13-,6,14-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-, 8,9-, 8,10-,8,11-, 8,12-, 8,13-, 8,14-, 9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 10,11-,10,12-, 10,13-, 10,14-, 11,12-, 11,13-, 11,14-, 12,13-, 12,14- and13,14-dimethyl-2-ethylpentadecanoic acid; 3,4-, 3,5-, 3,6-, 3,7-, 3,8-,3,9-, 3,10-, 3,11-, 3,12-, 3,13-, 3,14-, 3,15-, 4,5-, 4,6-, 4,7-, 4,8-,4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 4,14-, 4,15-, 5,6-, 5,7-, 5,8-, 5,9-,5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 5,15-, 6,7-, 6,8-, 6,9-, 6,10-,6,11-, 6,12-, 6,13-, 6,14-, 6,15-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-,7,13-, 7,14-, 7,15-, 8,9-, 8,10-, 8,11-, 8,12-, 8,13-, 8,14-, 8,15-,9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 9,15-, 10,11-, 10,12-, 10,13-,10,14-, 10,15-, 11,12-, 11,13-, 11,14-, 11,15-, 12,13-, 12,14-, 12,15-,13,14-, 13,15- and 14,15-dimethyl-2-ethylhexadecanoic acid; and mixturesthereof;

(h) 3-, 4-, 5- and 6-, methyl-2-propylheptanoic acid; 3-, 4-, 5-, 6- and7-methyl-2-propyloctanoic acid; 3-, 4-, 5-, 6-, 7- and8-methyl-2-propylnonanoic acid; 3-, 4-, 5-, 6-, 7-, 8- and9-methyl-2-propyldecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, and10-methyl-2-propylundecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and11-methyl-2-propyldo decanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-and 12-methyl-2-propyltridecanoic acid; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-,11-, 12- and 13-methyl-2-propyltetradecanoic acid; 3-, 4-, 5-, 6-, 7-,8-, 9-, 10-, 11-, 12-, 13- and 14-methyl-2-propylpentadecanoic acid; andmixtures thereof;

(i) 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-,2,3,12-, 2,3,13-, 2,3,14-, 2,3,15-, 2,3,16-, 2,4,5-, 2,4,6-, 2,4,7-,2,4,8-, 2,4,9-, 2,4,10-, 2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-, 2,4,15-,2,4,16-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-,2,5,13-, 2,5,14-, 2,5,15-, 2,5,16-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,10-,2,6,11-, 2,6,12-, 2,6,13-, 2,6,14-, 2,6,15-, 2,6,16-, 2,7,8-, 2,7,9-,2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-, 2,7,15-, 2,7,16-, 2,8,9-,2,8,10-, 2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,8,15-, 2,8,16-, 2,9,10-,2,9,11-, 2,9,12-, 2,9,13-, 2,9,14-, 2,9,15-, 2,9,16-, 2,10,11-,2,10,12-, 2,10,13-, 2,10,14-, 2,10,15-, 2,10,16-, 2,11,12-, 2,11,13-,2,11,14-, 2,11,15-, 2,11,16-, 2,12,13-, 2,12,14-, 2,12,15-, 2,12,16-,2,13,14-, 2,13,15-, 2,13,16-, 2,14,15-, 2,14,16-, 2,15,16-, 3,4,5-,3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-,3,4,14-, 3,4,15-, 3,4,16-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-, 3,5,10-,3,5,11-, 3,5,12-, 3,5,13-, 3,5,14-, 3,5,15-, 3,5,16-, 3,6,7-, 3,6,8-,3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,6,13-, 3,6,14-, 3,6,15-, 3,6,16-,3,7,8-, 3,7,9-, 3,7,10-, 3,7,11-, 3,7,12-, 3,7,13-, 3,7,14-, 3,7,15-,3,7,16-, 3,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,8,13-, 3,8,15-, 3,8,14-,3,8,16-, 3,9,10-, 3,9,11-, 3,9,12-, 3,9,13-, 3,9,14-, 3,9,15-, 3,9,16-,3,10,11-, 3,10,12-, 3,10,13-, 3,10,14-, 3,10,15-, 3,10,16-, 3,11,12-,3,11,14-, 3,11,13-, 3,11,15-, 3,11,16-, 3,12,13-, 3,12,14-, 3,12,15-,3,12,16-, 3,13,14-, 3,13,15-, 3,13,16-, 3,14,15-, 3,14,16-, 3,15,16-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,5,13-,4,5,14-, 4,5,15-, 4,5,16-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-,4,6,12-, 4,6,13-, 4,6,14-, 4,6,15-, 4,6,16-, 4,7,8-, 4,7,9-, 4,7,10-,4,7,11-, 4,7,12-, 4,7,13-, 4,7,14-, 4,7,15-, 4,7,16-, 4,8,9-, 4,8,10-,4,8,11-, 4,8,13-, 4,8,14-, 4,8,15-, 4,8,16-, 4,9,10-, 4,9,11-, 4,9,12-,4,9,13-, 4,9,14-, 4,9,15-, 4,9,16-, 4,10,11-, 4,10,12-, 4,10,13-,4,10,14-, 4,10,15-, 4,10,16-, 4,11,12-, 4,11,13-, 4,11,14-, 4,11,15-,4,11,16-, 4,12,13, 4,12,14-, 4,12,15-, 4,12,16-, 4,13,14-, 4,13,15-,4,13,16-, 4,14,15-, 4,14,16-, 4,15,16-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-,5,6,11-, 5,6,12-, 5,6,13-, 5,6,14-, 5,6,15-, 5,6,16-, 5,7,8-, 5,7,9-,5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-, 5,7,14-, 5,7,15-, 5,7,16-, 5,8,9-,5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-, 5,8,14-, 5,8,15-, 5,8,16-, 5,9,10-,5,9,11-, 5,9,12-, 5,9,13-, 5,9,14-, 5,9,15-, 5,9,16-, 5,10,11-,5,10,12-, 5,10,13-, 5,10,14-, 5,10,15-, 5,10,16-, 5,11,12-, 5,11,13-,5,11,14-, 5,11,15-, 5,12,13-, 5,12,14-, 5,12,15-, 5,12,16-, 5,13,14-,5,13,15-, 5,13,16-, 5,14,15-, 5,14,16-, 5,15,16-, 6,7,8-, 6,7,9-,6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-, 6,7,15-, 6,7,16-, 6,8,9-,6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,8,15-, 6,8,16-, 6,9,10-,6,9,11-, 6,9,12-, 6,9,13-, 6,9,14-, 6,9,15-, 6,9,16-, 6,10,11-,6,10,12-, 6,10,13-, 6,10,14-, 6,10,15-, 6,10,16-, 6,11,12-, 6,11,13-,6,11,14-, 6,11,15-, 6,11,16-, 6,12,13-, 6,12,14-, 6,12,15-, 6,12,16-,6,13,14-, 6,13,15-, 6,13,16-, 6,14,15-, 6,14,16-, 6,15,16-, 7,8,9-,7,8,10-, 7,8,11-, 7,8,12-, 7,8,13-, 7,8,14-, 7,8,15-, 7,8,16-, 7,9,10-,7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-, 7,9,15-, 7,9,16-, 7,10,11-,7,10,12-, 7,10,13-, 7,10,14-, 7,10,15-, 7,10,16-, 7,11,12-, 7,11,13-,7,11,14-, 7,11,15-, 7,11,16-, 7,12,13-, 7,12,14-, 7,12,15-, 7,12,16-,7,13,14-, 7,13,15-, 7,13,16-, 7,14,15-, 7,14,16-, 7,15,16-, 8,9,10-,8,9,11-, 8,9,12-, 8,9,13-, 8,9,14-, 8,9,15-, 8,9,16-, 8,10,11-,8,10,12-, 8,10,13-, 8,10,14-, 8,10,15-, 8,10,16-, 8,11,12-, 8,11,13-,8,11,14-, 8,11,15-, 8,11,16-, 8,12,13-, 8,12,14-, 8,12,15-, 8,12,16-,8,13,14-, 8,13,15-, 8,13,16-, 8,14,15-, 8,14,16-, 8,15,16-, 9,10,11-,9,10,12-, 9,10,13-, 9,10,14-, 9,10,15-, 9,10,16-, 9,11,12-, 9,11,13-,9,11,14-, 9,11,15-, 9,11,16-, 9,12,13-, 9,12,14-, 9,12,15-, 9,12,16-,9,13,14-, 9,13,15-, 9,13,16-, 9,14,15-, 9,14,16-, 9,15,16-, 10,11,12-,10,11,13-, 10,11,14-, 10,11,15-, 10,11,16-, 10,12,13-, 10,12,14-,10,12,15-, 10,12,16-, 10,13,14-, 10,13,15-, 10,13,16-, 10,14,15-,10,14,16-, 10,15,16-, 11,12,13-, 11,12,14-, 11,12,15-, 11,12,16-,11,13,14-, 11,13,15-, 11,13,16-, 11,14,15-, 11,14,16-, 11,15,16-,12,13,14-, 12,13,15-, 12,13,16-, 12,14,15-, 12,14,16-, 12,15,16-,13,14,15-, 13,14,16-, 13,15,16- and 14,15,16-trimethethylheptadecanoicacid; 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-,2,3,13-, 2,3,14-, 2,3,15-, 2,4,5-, 2,4,6-, 2,4,7-, 2,4,9-, 2,4,10-,2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-, 2,4,15-, 2,5,6-, 2,5,7-, 2,5,8-,2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,5,13-, 2,5,14-, 2,5,15-, 2,6,7-,2,6,8-, 2,6,9-, 2,6,10-, 2,6,11-, 2,6,12-, 2,6,13-, 2,6,14-, 2,6,15-,2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-, 2,7,15-,2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,8,15-, 2,9,10-,2,9,11-, 2,9,12-, 2,9,13-, 2,9,14-, 2,9,15-, 2,10,11-, 2,10,12-,2,10,13-, 2,10,14-, 2,10,15-, 2,11,12-, 2,11,13-, 2,11,14-, 2,11,15-,2,12,13-, 2,12,14-, 2,12,15-, 2,13,14-, 2,13,15-, 2,14,15-, 3,4,5-,3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-,3,4,14-, 3,4,15-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-, 3,5,10-, 3,5,11-,3,5,12-, 3,5,13-, 3,5,14-, 3,5,15-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-,3,6,11-, 3,6,12-, 3,6,13-, 3,6,14-, 3,6,15-, 3,7,8-, 3,7,9-, 3,7,10-,3,7,11-, 3,7,12-, 3,7,13-, 3,7,14-, 3,7,15-, 3,8,9-, 3,8,10-, 3,8,11-,3,8,12-, 3,8,13-, 3,8,14-, 3,8,15-, 3,9,10-, 3,9,11-, 3,9,12-, 3,9,13-,3,10,11-, 3,10,12-, 3,10,13-, 3,10,14-, 3,10,15-, 3,11,12-, 3,11,13-,3,11,14-, 3,11,15-, 3,12,13-, 3,12,14-, 3,12,15-, 3,13,14-, 3,13,15-,3,14,15-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-,4,5,13-, 4,5,14-, 4,5,15-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-,4,6,12-, 4,6,13-, 4,6,14-, 4,6,15-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-,4,7,12-, 4,7,13-, 4,7,14-, 4,7,15-, 4,8,9-, 4,8,10-, 4,8,11-, 4,8,12-,4,8,13-, 4,8,14-, 4,8,15-, 4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-, 4,9,14-,4,9,15-, 4,10,11-, 4,10,12-, 4,10,13-, 4,10,14-, 4,10,15-, 4,11,12-,4,11,13-, 4,11,14-, 4,11,15-, 4,12,13-, 4,12,14-, 4,12,15-, 4,13,14-,4,13,15-, 4,14,15-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-,5,6,13-, 5,6,14-, 5,6,15-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-,5,7,13-, 5,7,14-, 5,7,15-, 5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-,5,8,14-, 5,8,15-, 5,9,10-, 5,9,11-, 5,9,12-, 5,9,13-, 5,9,14-, 5,9,15-,5,10,11-, 5,10,12-, 5,10,13-, 5,10,14-, 5,10,15-, 5,11,12-, 5,11,13-,5,11,14-, 5,11,15-, 5,12,13-, 5,12,14-, 5,12,15-, 5,13,14-, 5,13,15-,5,14,15-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-,6,7,15-, 6,8,9-, 6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,8,15-,6,9,10-, 6,9,11-, 6,9,12-, 6,9,13-, 6,9,14-, 6,9,15-, 6,10,11-,6,10,12-, 6,10,13-, 6,10,14-, 6,10,15-, 6,11,12-, 6,11,13-, 6,11,14-,6,11,15-, 6,12,13-, 6,12,14-, 6,12,15-, 6,13,14-, 6,13,15-, 6,14,15-,7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-, 7,8,13-, 7,8,14-, 7,8,15-, 7,9,10-,7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-, 7,9,15-, 7,10,11-, 7,10,12-,7,10,13-, 7,10,14-, 7,10,15-, 7,11,12-, 7,11,13-, 7,11,14-, 7,11,15-,7,12,13-, 7,12,14-, 7,12,15-, 7,13,14-, 7,13,15-, 7,14,15-, 8,9,10-,8,9,11-, 8,9,12-, 8,9,13-, 8,9,14-, 8,9,15-, 8,10,11-, 8,10,12-,8,10,13-, 8,10,14-, 8,10,15-, 8,11,12-, 8,11,13-, 8,11,14-, 8,11,15-,8,12,13-, 8,12,14-, 8,12,15-, 8,13,14-, 8,13,15-, 8,14,15-, 9,10,11-,9,10,12-, 9,10,13-, 9,10,14-, 9,10,15-, 9,11,12-, 9,11,13-, 9,11,14-,9,11,15-, 9,12,13-, 9,12,14-, 9,12,15-, 9,13,14-, 9,13,15-, 9,14,15-,10,11,12-, 10,11,13-, 10,11,14-, 10,11,15-, 10,12,13-, 10,12,14-,10,12,15-, 10,13,14-, 10,13,15-, 10,14,15-, 11,12,13-, 11,12,14-,11,12,15-, 11,13,14-, 11,13,15-, 11,14,15-, 12,13,14-, 12,13,15-,12,14,15- and 4,15-trimethylhexadecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-,2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-, 2,3,13-, 2,3,14-,2,4,5-, 2,4,7-, 2,4,9-, 2,4,10-, 2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-,2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,5,13-,2,5,14-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,10-, 2,6,11-, 2,6,12-, 2,6,13-,2,6,14-, 2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-,2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,9,10-, 2,9,11-,2,9,12-, 2,9,13-, 2,9,14-, 2,10,11-, 2,10,12-, 2,10,13-, 2,10,14-,2,11,12-, 2,11,13-, 2,11,14-, 2,12,13-, 2,12,14-, 2,13,14-, 3,4,5-,3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-,3,4,14-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,10-, 3,5,11-, 3,5,12-, 3,5,13-,3,5,14-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,6,13-,3,6,14-, 3,7,8-, 3,7,10-, 3,7,12-, 3,7,13-, 3,7,14-, 3,8,9-, 3,8,10-,3,8,11-, 3,8,12-, 3,8,13-, 3,8,14-, 3,9,10-, 3,9,12-, 3,9,13-, 3,9,14-,3,10,11-, 3,10,12-, 3,10,13-, 3,10,14-, 3,11,12-, 3,11,13-, 3,11,14-,3,12,13-, 3,12,14-, 3,13,14-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-,4,5,11-, 4,5,12-, 4,5,13-, 4,5,14-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-,4,6,11-, 4,6,12-, 4,6,13-, 4,6,14-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-,4,7,12-, 4,7,13-, 4,7,14-, 4,8,9-, 4,8,10-, 4,8,11-, 4,8,12-, 4,8,13-,4,8,14-, 4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-, 4,9,14-, 4,10,11-,4,10,12-, 4,10,13-, 4,10,14-, 4,11,12-, 4,11,13-, 4,11,14-, 4,12,13-,4,12,14-, 4,13,14-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-,5,6,13-, 5,6,14-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-,5,7,14-, 5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-, 5,8,14-, 5,9,10-,5,9,11-, 5,9,12-, 5,9,13-, 5,9,14-, 5,10,11-, 5,10,12-, 5,10,13-,5,10,14-, 5,11,12-, 5,11,13-, 5,11,14-, 5,12,13-, 5,12,14-, 5,13,14-,6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-, 6,8,9-,6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,9,10-, 6,9,11-, 6,9,12-,6,9,13-, 6,9,14-, 6,10,11-, 6,10,12-, 6,10,13-, 6,11,12-, 6,11,13-,6,11,14-, 6,12,13-, 6,12,14-, 6,13,14-, 7,8,9-, 7,8,10-, 7,8,11-,7,8,12-, 7,8,13-, 7,8,14-, 7,9,10-, 7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-,7,10,11-, 7,10,12-, 7,10,13-, 7,10,14-, 7,11,12-, 7,11,13-, 7,11,14-,7,12,13-, 7,12,14-, 7,13,14-, 8,9,10-, 8,9,11-, 8,9,12-, 8,9,13-,8,9,14-, 8,10,11-, 8,10,12-, 8,10,13-, 8,10,14-, 8,11,12-, 8,11,13-,8,11,14-, 8,12,13-, 8,12,14-, 8,13,14-, 9,10,11-, 9,10,12-, 9,10,13-,9,10,14-, 9,11,12-, 9,11,13-, 9,11,14-, 9,12,13-, 9,12,14-, 9,13,14-,10,11,12-, 10,11,13-, 10,11,14-, 10,12,13-, 10,12,14-, 10,13,14-,11,12,13-, 11,12,14-, 11,13,14- and 12,13,14-trimethylpentadecanoicacid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-,2,3,12-, 2,3,13-, 2,4,5-, 2,4,7-, 2,4,9-, 2,4,10-, 2,4,11-, 2,4,12-,2,4,13-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-,2,5,13-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,11-, 2,6,12-, 2,6,13-, 2,7,8-,2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,8,9-, 2,8,10-, 2,8,11-,2,8,12-, 2,8,13-, 2,9,10-, 2,9,11-, 2,9,12-, 2,9,13-, 2,10,11-,2,10,12-, 2,10,13-, 2,11,12-, 2,11,13-, 2,12,13-, 3,4,5-, 3,4,6-,3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-, 3,5,6-,3,5,7-, 3,5,8-, 3,5,9-, 3,5,10-, 3,5,11-, 3,5,12-, 3,5,13-, 3,6,7-,3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,7,8-, 3,7,10-, 3,7,11-,3,7,12-, 3,7,13-, 3,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,8,13-, 3,9,10-,3,9,11-, 3,9,12-, 3,9,13-, 3,10,11-, 3,10,12-, 3,10,13-, 3,11,12-,3,11,13-, 3,12,13-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-,4,5,12-, 4,5,13-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-, 4,6,12-,4,6,13-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,7,12-, 4,7,13-, 4,8,9-,4,8,10-, 4,8,11-, 4,8,12-, 4,8,13-, 4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-,4,10,11-, 4,10,12-, 4,10,13-, 4,11,12-, 4,11,13-, 4,12,13-, 5,6,7-,5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-, 5,6,13-, 5,7,8-, 5,7,9-,5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-, 5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-,5,8,13-, 5,9,10-, 5,9,11-, 5,9,12-, 5,10,11-, 5,10,12-, 5,10,13-,5,11,12-, 5,11,13-, 5,12,13-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-,6,7,13-, 6,8,9-, 6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,9,10-, 6,9,11-,6,9,12-, 6,9,13-, 6,10,11-, 6,10,12-, 6,10,13-, 6,11,12-, 6,11,13-,6,12,13-, 7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-, 7,8,13-, 7,9,10-, 7,9,11-,7,9,12-, 7,9,13-, 7,10,11-, 7,10,12-, 7,10,13-, 7,11,12-, 7,11,13-,7,12,13-, 8,9,10-, 8,9,11-, 8,9,12-, 8,9,13-, 8,10,11-, 8,10,12-,8,10,13-, 8,11,12-, 8,11,13-, 8,12,13-, 9,10,11-, 9,10,12-, 9,10,13-,9,11,12-, 9,11,13-, 9,12,13-, 10,11,12-, 10,11,13-, 10,12,13- and11,12,13-trimethyltetradecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-,2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-, 2,4,5-, 2,4,7-, 2,4,9-,2,4,11-, 2,4,12-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-,2,5,12-, 2,6,7-, 2,6,8-, 2,6,9-, 2,6,11-, 2,6,12-, 2,7,8-, 2,7,9-,2,7,10-, 2,7,11-, 2,7,12-, 2,8,9-, 2,8,10-, 2,8,11-, 2,8,12-, 2,9,10-,2,9,11-, 2,9,12-, 2,10,11-, 2,10,12-, 2,11,12-, 3,4,5-, 3,4,6-, 3,4,7-,3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,4,12-, 3,5,6-, 3,5,7-, 3,5,8-,3,5,10-, 3,5,11-, 3,5,12-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-,3,6,12-, 3,7,8-, 3,7,10-, 3,7,11-, 3,7,12-, 3,8,9-, 3,8,10-, 3,8,11-,3,8,12-, 3,9,10-, 3,9,11-, 3,9,12-, 3,10,11-, 3,10,12-, 3,11,12-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,6,7-,4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-, 4,6,12-, 4,7,8-, 4,7,9-, 4,7,10-,4,7,11-, 4,7,12-, 4,8,9-, 4,8,10-, 4,8,11-, 4,9,10-, 4,9,11-, 4,9,12-,4,10,11-, 4,10,12-, 4,11,12-, 5,6,7-, 5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-,5,6,12-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,8,9-, 5,8,10-,5,8,11-, 5,8,12-, 5,9,10-, 5,9,11-, 5,9,12-, 5,10,11-, 5,10,12-,5,11,12-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,8,9-, 6,8,10-,6,8,11-, 6,8,12-, 6,9,10-, 6,9,11-, 6,9,12-, 6,10,11-, 6,10,12-,6,11,12-, 7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-, 7,9,10-, 7,9,11-, 7,9,12-,7,10,11-, 7,10,12-, 7,11,12-, 8,9,10-, 8,9,11-, 8,9,12-, 8,10,11-,8,10,12-, 8,11,12-, 9,10,11-, 9,10,12-, 9,11,12- and10,11,12-trimethyltridecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-,2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,4,5-, 2,4,7-, 2,4,9-, 2,4,10-,2,4,11-, 2,5,6-, 2,5,7-, 2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,6,7-,2,6,8-, 2,6,9-, 2,6,11-, 2,7,8-, 2,7,9-, 2,7,10-, 2,7,11-, 2,8,9-,2,8,10-, 2,8,11-, 2,9,10-, 2,9,11-, 2,10,11-, 3,4,5-, 3,4,6-, 3,4,7-,3,4,8-, 3,4,9-, 3,4,10-, 3,4,11-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-,3,5,10-, 3,5,11-, 3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,7,8-,3,7,9-, 3,7,10-, 3,8,9-, 3,8,10-, 3,8,11-, 3,9,10-, 3,9,11-, 3,10,11-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,6,7-, 4,6,8-,4,6,9-, 4,6,10-, 4,6,11-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,8,9-,4,8,10-, 4,8,11-, 4,9,10-, 4,9,11-, 4,10,11-, 5,6,7-, 5,6,8-, 5,6,9-,5,6,10-, 5,6,11-, 5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,8,9-, 5,8,10-,5,8,11-, 5,9,10-, 5,9,11-, 5,10,11-, 6,7,8-, 6,7,9-, 6,7,10-, 6,7,11-,6,8,9-, 6,8,10-, 6,8,11-, 6,9,10-, 6,9,11-, 6,10,11-, 7,8,9-, 7,8,10-,7,8,11-, 7,9,10-, 7,9,11-, 7,10,11-, 8,9,10-, 8,9,11-, 8,10,11- and9,10,11-trimethyldodecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-, 2,3,7-,2,3,8-, 2,3,9-, 2,3,10-, 2,4,7-, 2,4,9-, 2,4,10-, 2,5,6-, 2,5,7-,2,5,8-, 2,5,9-, 2,5,10-, 2,6,7-, 2,6,9-, 2,7,8-, 2,7,9-, 2,7,10-,2,8,9-, 2,8,10-, 2,9,10-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-,3,4,10-, 3,5,6-, 3,5,8-, 3,5,9-, 3,5,10-, 3,6,7-, 3,6,8-, 3,6,9-,3,6,10-, 3,7,8-, 3,7,9-, 3,7,10-, 3,8,9-, 3,8,10-, 3,9,10-, 4,5,6-,4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-,4,7,8-, 4,7,9-, 4,7,10-, 4,8,9-, 4,8,10-, 4,9,10-, 5,6,7-, 5,6,8-,5,6,9-, 5,6,10-, 5,7,8-, 5,7,9-, 5,7,10-, 5,8,9-, 5,8,10-, 5,9,10-,6,7,8-, 6,7,9-, 6,7,10-, 6,8,9-, 6,8,10-, 6,9,10-, 7,8,9-, 7,8,10-,7,9,10- and 8,9,10-trimethylundecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-,2,3,7-, 2,3,8-, 2,3,9-, 2,4,5-, 2,4,7-, 2,4,9-, 2,5,6-, 2,5,7-, 2,5,8-,2,6,7-, 2,6,9-, 2,7,8-, 2,7,9-, 2,8,9-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-,3,4,9-, 3,5,6-, 3,5,7-, 3,5,8-, 3,5,9-, 3,6,7-, 3,6,8-, 3,6,9-, 3,7,8-,3,7,9-, 3,8,9-, 4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,6,7-, 4,6,9-, 4,7,8-,4,7,9-, 4,8,9-, 5,6,7-, 5,6,8-, 5,6,9-, 5,7,8-, 5,7,9-, 5,8,9-, 6,7,8-,6,7,9-, 6,8,9- and 7,8,9-trimethyldecanoic acid; 2,3,4-, 2,3,5-, 2,3,6-,2,3,7-, 2,3,8-, 2,4,5-, 2,4,6-, 2,4,7-, 2,4,8-, 2,5,6-, 2,5,7-, 2,5,8-,2,6,7-, 2,6,8-, 2,7,8-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,5,6-, 3,5,7-,3,5,8-, 3,6,7-, 3,6,8-, 3,7,8-, 4,5,6-, 4,5,7-, 4,5,8-, 4,6,7-, 4,6,8-,4,7,8-, 5,6,7-, 5,6,8-, 5,7,8- and 6,7,8-trimethylnonanoic acid; andmixtures thereof;

(j) 3-butyl-4-ethyl, 3-pentyl-4-propyl, 3-butyl-4-propyl and3-pentyl-4-ethylheptanoic acid; 3-butyl-4-methyl, 4-propyl-5-ethyl,5-ethyl-6-propyl, 3-pentyl-4-ethyl, 4-butyl-5-propyl, 3-hexyl-4-propyl,3-pentyl-4-methyl, 3-butyl-4-ethyl, 4-butyl-5-ethyl, 4,5-dipropyl,3-pentyl-4-propyl, 3-hexyl-4-ethyl, 3-hexyl-4-butyl and3-heptyl-4-propyloctanoic acid; 4-propyl-5-methyl, 3-pentyl-4-methyl,4-butyl-5-ethyl, 5,6,dipropyl, 3-hexyl-4-ethyl, 4-pentyl-5-propyl,3-heptyl-4-propyl, 3-butyl-4-methyl, 4-butyl-5-methyl, 4-propyl-5-ethyl,5-ethyl-6-propyl, 5-propyl-6-ethyl, 3-hexyl-4-methyl, 3-pentyl-4-ethyl,4-pentyl-5-ethyl, 4-butyl-5-propyl, 3-hexyl-4-propyl, 4-pentyl-5-butyland 4-hexyl-5-propylnonanoic acid; 5-ethyl-6-methyl, 6-methyl-7-ethyl,4-butyl-5-methyl, 4-pentyl-5-ethyl, 5-butyl-6-propyl, 4-propyl-5-methyl,5,6-diethyl, 6,7-diethyl, 3-pentyl-4-methyl, 4-pentyl-5-methyl,6-ethyl-7-propyl, 5-propyl-6-ethyl, 3-hexyl-4-methyl, 3-heptyl-4-ethyl,4-hexyl-5-propyl, 4-butyl-5-ethyl, 6-methyl-7-propyl, 5-propyl-6-methyl,5-butyl-6-ethyl, 3-heptyl-4-methyl, 3-hexyl-4-ethyl, 4-hexyl-5-ethyl,4-pentyl-5-propyl, 5,6-dibutyl, 5-pentyl-6-propyl and3-heptyl-4-methyldecanoic acid; 5-propyl-6-methyl, 6,7-diethyl,7-methyl-8-propyl, 4-pentyl-5-methyl, 5-butyl-6-ethyl, 6,7-dipropyl,3-heptyl-4-methyl, 4-hexyl-5-ethyl, 5-pentyl-6-propyl, 6-methyl-7-ethyl,6-ethyl-7-methyl, 5-ethyl-6-methyl, 7-methyl-8-ethyl, 5-butyl-6-methyl,4-butyl-5-methyl, 6-ethyl-7-propyl, 6-propyl-7-ethyl, 3-hexyl-4-methyl,4-hexyl-5-methy, 4-pentyl-5-ethyl, 5-pentyl-6-ethyl, 6-propyl-7-butyland 6-butyl-7-propylundecanoic acid; 5-pentyl-6-methyl, 6,7-diethyl,7,8-diethyl, 6-ethyl-7-methyl, 7-methyl-8-ethyl, 5-butyl-6-methyl,7-ethyl-8-propyl, 6-propyl-7-ethyl, 4-hexyl-5-methyl, 5-pentyl-6-ethyl,7-methyl-8-propyl, 6-propyl-7-methyl, 4-pentyl-5-methyl,7-ethyl-8-butyl, 6-butyl-7-ethyl, 6-butyl-7-ethyl, 5-butyl-6-ethyl,6,7-dipropyl and 7,8-dipropyldodecanoic acid; 7-ethyl-8-propyl,7-propyl-8-ethyl, 7,8-dipropyl, 7,8-diethyl, 8-methyl-9-propyl,6-propyl-7-methyl, 5-pentyl-6-methyl, 7-methyl-8-ethyl,6-ethyl-7-methyl, 8-methyl-8-ethyl, 8-methyl-9-butyl, 6-butyl-7-methyl,6-butyl-7-methyl, 5-butyl-6-methyl, 6-propyl-7-ethyl and8-ethyl-9-propyltridecanoic acid; 6-propyl-7-methyl, 9-methyl-10-propyl,8-ethyl-9-propyl, 7-ethyl-8-methyl, 7-propyl-8-ethyl, 8-methyl-9-ethyl,8-methyl-9-propyl, 7-propyl-8-methyl, 7,8-diethyl and8,9-diethyltetradecanoic acid; 8,9-diethyl, 9-methyl-10-propyl,7-propyl-8-methyl, 8-methyl-9-ethyl, 8-ethyl-9-methyl, 7-ethyl-8-methyland 9-methyl-10-ethylpentadecanoic acid; 8-ethyl-9-methyl and9-methyl-10-ethylhexadecanoic acid; and mixtures thereof;

(k) mixtures of (a) to (j);

This composition of matter, when added to consumer product formulations,have many valuable effects and uses including, for example, assurfactants, cosurfactants, foam boosters, suds suppressors, calciumsequestrants/limesoap dispersants, crystal growth modifiers for thecalcium soaps of straight-chain fatty acids, as consumer productphysical property modifiers (for example as viscosity modifiers forliquid detergents), as soil modifiers for improving the removability ofsoil from a substrate, as dual-functional cleaning/care materials, asfungicides or antimicrobials, as consumer product dissolution aids, andas skin or hair feel improvement agents. Other uses, depending on thespecific compounds used, include fabric softening and paper productformulation.

In a second embodiment of the invention, the branched carboxylic acid inthe composition of matter can form one or more ester or amide linkageswith a compound containing a nitrogen, preferably quaternary nitrogen,atom to produce fabric softening actives. Specifically, the activespreferably have the formulas:

[(R)_(4−m)—N⁽⁺⁾—[(CH₂)_(n)—Y—R¹]_(m)]X⁽⁻⁾  1)

wherein each R substituent is hydrogen or a short chain C₁-C₆,preferably C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl (mostpreferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, ormixtures thereof; each m is 2 or 3, preferably 2; each n is from 1 toabout 4, preferably 2; each Y is —O—(O)C— or —(R)N—(O)C— preferably—O—(O)C—; the sum of carbons in each R¹, plus one when Y is —O—(O)C— or—(R)N—(O)C— (“YR¹ sum”), is C₆-C₂₂, preferably C₁₂₋₂₂, more preferablyC₁₄-C₂₀, (hereinafter, R¹ and YR¹ are used interchangeably to representthe hydrophobic chain, the R¹ chain lengths in general being evennumbered for fatty alcohols and odd for fatty acids), but no more thanone YR¹ sum being less than about 12 and then the other R¹, or YR¹, sumis at least about 16, with each R¹ comprising a long chain C₅-C₂₁ (orC₆-C₂₂), preferably C₁₀-C₂₀ (or C₉-C₁₉) unsaturated alkyl, mostpreferably C₁₂-C₁₈ (or C₁₁-C₁₇) unsaturated alkyl, or at lest one of thebranched carboxylic acid in the composition of matter the ratio of thebranched carboxylic acid to unsaturated alkyl being from about 1:0 toabout 5:95, preferably from about 75:25 to about 25:75, more preferablyfrom about 50:50 to about 30:70, and for the unsaturated alkyl group,the Iodine Value of the parent fatty acid of this R¹ group is preferablyfrom about 20 to about 140, more preferably from about 50 to about 130;and most preferably from about 70 to about 115 and wherein thecounterion, X⁻, can be any softener-compatible anion, preferably,chloride, bromide, methylsulfate, ethylsulfate, sulfate, and/or nitrate,more preferably chloride and/or methylsulfate;

wherein each Y, R, R¹, and X⁽⁻⁾ have the same meanings as before (Suchcompounds include those having the formula:

[CH₃]₃N⁽⁺⁾[CH₂CH(CH₂O(O)CR¹)O(O)CR¹]C1⁽⁻⁾

where —O—(O)CR¹ is derived partly from unsaturated, e.g., oleic, fattyacid and, preferably, each R is a methyl or ethyl group and preferablyeach R¹ is in the range of C₁₅ to C₁₉;

[R_(4−m)—N⁽⁺⁾—R¹ _(m)](X)⁻  3)

wherein each m is 2 or 3, R¹ and X⁻ have the same meanings as before;

wherein each R, R¹, and X⁻ have the definitions given above; each R² isa C₁₋₆ alkylene group, preferably an ethylene group; and G is an oxygenatom or an —NR— group;

wherein R¹, R² and G are defined as above;

6) reaction products of substantially unsaturated and/or branched chainhigher fatty acids with dialkylenetriamines in, e.g., a molecular ratioof about 2:1, said reaction products containing compounds of theformula:

R¹—C(O)—NH—R²—NH—R³—NH—C(O)—R¹

wherein R¹, R² are defined as above, and each R³ is a C₁₋₆ alkylenegroup, preferably an ethylene group;

[R¹—C(O)—NR—R²—N(R)₂—R³—NR—C(O)—R¹]⁺X⁻  7)

wherein R, R¹, R², R³ and X⁻ are defined as above;

8) the reaction product of substantially unsaturated and/or branchedchain higher fatty acid with hydroxyalkylalkylenediarnines in amolecular ratio of about 2:1, said reaction products containingcompounds of the formula:

R¹—C(O)—NH—R²—N(R³OH)—C(O)—R¹

wherein R¹, R² and R³ are defined as above;

wherein R, R¹, R², and X⁻ are defined as above;

10) acyclic quaternary ammonium salts having the formula:

[R¹—N(R⁵)₂—R⁶]⁺X⁻

wherein R⁵ and R⁶ are C₁-C₄ alkyl or hydroxyalkyl groups, and R¹ and X⁻are defined as herein above;

11) substituted imidazolinium salts having the formula:

wherein R⁷ is hydrogen or a C₁-C₄ saturated alkyl or hydroxyalkyl group,and R¹ and X⁻ are defined as hereinabove;

12) substituted imidazolinium salts having the formula:

wherein R⁵ is a C₁-C₄ alkyl or hydroxyalkyl group, and R¹, R², and X⁻are as defined above;

13) alkylpyridinium salts having the formula:

wherein R¹ and X⁻ are defined as herein above;

14) alkanamide alkylene pyridinium salts having the formula:

wherein R¹, R² and X⁻ are defined as herein above; and

15) mixtures thereof.

The above compounds preferably have a phase transition temperature ofless than about 50° C., more preferably less than about 35° C., evenmore preferably less than about 20° C., and yet even more preferablyless than about 0° C. Fabric softening compounds having such phasetransition temperatures are easier to process, provide fabrics havingimproved water absorption properties, and provide superior fabric feel.

The present invention also relates to fabric softening compositionscontaining, as an essential component, from about 2% to about 80%,preferably from about 13% to about 75%, more preferably from about 15%to about 70%, and even more preferably from about 19% to about 65%, byweight of the composition, of said fabric softener actives, said fabricsoftener actives being selected from the compounds identifiedhereinbefore, and mixtures thereof. These fabric softening compositionscontains:

A) from about 2% to about 80%, preferably from about 13% to about 75%,more preferably from about 15% to about 70%, and even more preferablyfrom about 19% to about 65%, by weight of the composition, ofbiodegradable fabric softener active identified hereinbefore

B) optionally, but preferably, the compositions can also contain aneffective amount to improve clarity, less than about 40%, morepreferably from about 10% to about 35%, more preferably from about 12%to about 25%, and even more preferably from about 14% to about 20%, byweight of the composition of principal solvent having a ClogP of fromabout −2.0 to about 2.6, more preferably from about −1.7 to about 1.6,and even more preferably from about −1.0 to about 1.0, as definedhereinafter” said principal solvent preferably selected from the groupconsisting of: 2,2,4-trimethyl-1,3-pentane diol; the ethoxylate,diethoxylate, or triethoxylate derivatives of2,2,4-trimethyl-1,3-pentane diol; 2-ethylhexyl-1,3-diol; the ethoxylate,diethoxylate, or triethoxylate derivatives of 2-ethylhexyl-1,3-diol; 1,2hexanediol; hexylene glycol; and mixtures thereofto provide a clearproduct;

C) optionally, but preferably, an effective amount, sufficient toimprove clarity, of low molecular weight water soluble solvents likeethanol, isopropanol, propylene glycol, 1,3-propanediol, propylenecarbonate, etc., said water soluble solvents being at a level that willnot form clear compositions by themselves;

D) optionally, but preferably, an effective amount to improve clarity,of water soluble calcium and/or magnesium salt, preferably chloride; and

E) the balance being water.

Preferably, the fabric softening compositions herein are aqueous,translucent or clear, preferably clear, compositions containing fromabout 3% to about 95%, preferably from about 10% to about 80%, morepreferably from about 30% to about 70%, and even more preferably fromabout 40% to about 60%, water and from about 3% to about 40%, preferablyfrom about 10% to about 35%, more preferably from about 12% to about25%, and even more preferably from about 14% to about 20%, of the aboveprincipal alcohol solvent B. These preferred products (fabric softeningcompositions) are not translucent, or clear, without principal solventB. The amount of principal solvent B required to make the compositionstranslucent, or clear, is preferably more than 50%, more preferably morethan about 60%, and even more preferably more than about 75%, of thetotal organic solvent present.

The fabric softening compositions can also be prepared as conventionaldispersions of the fabric softener active containing from about 2% toabout 50%, preferably from about 10% to about 40%, more preferably fromabout 15% to about 30%, of the fabric softener active. The fabricsoftening compositions can also be prepared as solids, either granular,or attached to substrates, as disclosed hereinafter.

The pH of the aqueous fabric softening compositions should be from about1 to about 7, preferably from about 1.5 to about 5, more preferably fromabout 2 to about 3.5.

All percentages and proportions herein are by weight unless otherwiseindicated. All documents are incorporated, in their relevant part, byreference.

DETAILED DESCRIPTION OF THE INVENTION

Highly preferred for the purpose of consumer cleaning products such aslaundry detergents and personal care compositions of the invention, arethe fatty acids and the salts identified hereinabove. The esters are notcomparable in their utility for such products but may be useful asintermediates and in fabric conditioners and non-laundry applicationsalso described herein.

As used herein the term branched carboxylic acid includes not only thebranched carboxylic acid but also any stereoisomers, lower alkyl esters(preferably C₁-C₃, more preferably methyl esters) and salts (preferablysodium, potassium, ammonium, substituted ammonium, aluminum, zinc,calcium and magnesium salts). The composition of matter may also includemixtures, see herein after, for example, mixtures of acid, esters andsalts with different or identical carbon chains. The composition ofmatter herein can be used alone, in mixtures with each other in anyproportion, or in mixtures with any known (conventional) materials suchas those disclosed in the background. We distinguish herein between (I)levels of any inventive compound in, on one hand, a mixture containingonly the composition of matter or its mixtures with other conventionalfatty acids or their derivatives and (II) levels of any composition ofmatter, or mixture containing same, in a fully-formulated consumerproduct. In terms of (I), levels suitable herein are typically about 1%or higher, preferably 5% or higher, more preferably 10% or higher, andcommonly up to about 51% to 99.9%.

The invention also encompasses mixtures of the composition of matter(s)with known materials, i.e., levels are of the type (II). Suchcompositions include a composition comprising (new material) (i) fromabout 5% to about 99.9% of compounds according to any one or more of theten aspects defined above; said composition further comprising(conventional material) (ii) from about 5% to about 95% of conventionalcompounds selected from linear fatty acid compounds or the C1-C3 alkylesters (preferably methyl esters) or salts (preferably sodium,potassium, ammonium, substituted ammonium, aluminum, zinc, calcium andmagnesium salts) of any of said (conventional) compounds. Alternatively,the conventional linear materials can be replaced by, or mixed with toprovide comparable proportions, conventional alkyl-substituted fattyacid compounds or the stereoisomers, C1-C3 alkyl esters (preferablymethyl esters) and salts (preferably sodium, potassium, ammonium,substituted ammonium, aluminum, zinc, calcium and magnesium salts) ofany of said (conventional alkyl-substituted) compounds; and mixturesthereof.

To further illustrate, conventional alkyl-substituted fatty acidcompounds (see background) permit the present invention to include amixture of composition of the matter and further comprising from about0.1% to about 95% of said conventional compounds, (ii), selected fromthe group consisting of: 2-methyl, 3-methyl, 4-methyl, 5-methyl,6-methyl, 7-,methyl, 8-methyl and 9-methyldecanoic acid; 2-methyl,3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl, 9-methyl and10-methylundecanoic acid; 2-methyl, 3-methyl, 4-methyl, 5-methyl,6-methyl, 7-methyl, 8-methyl, 9-methyl, 10-methyl and11-methyldodecanoic acid; 2-methyl, 3-methyl, 4-methyl, 5-methyl,8-methyl, 9-methyl, 11-methyl and 12-methyltridecanoic acid; 2-methyl,3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl, 9-methyl,10-methyl, 11-methyl, 12-methyl and 13-methyltetradecanoic acid;2-methyl, 3-methyl, 4-methyl, 6-methyl, 7-methyl, 10-methyl, 11-methyl,12-methyl, 13-methyl and 14-methylpentadecanoic acid; 2-methyl,3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl, 9-methyl,10-methyl, 11-methyl, 12-methyl, 13-methyl, 14-methyl and15-methylhexadecanoic acid; 2-methyl, 3-methyl, 4-methyl, 5-methyl,6-methyl, 7-methyl, 8-methyl, 9-methyl, 10-methyl, 11-methyl, 12-methyl,13-methyl, 14-methyl, 15-methyl and 16-methylheptadecanoic acid;2-methyl, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 7-methyl, 8-methyl,9-methyl, 10-methyl, 11-methyl, 12-methyl, 13-methyl, 14-methyl,15-methyl, 16-methyl and 17-methyloctadecanoic acid; 2-methyl, 3-methyl,4-methyl, 10-methyl, 17-methyl and 18-methylnonadecanoic acid; and thestereoisomers, C1-C3 alkyl esters (preferably methyl esters) and salts(preferably sodium, potassium, ammonium, substituted ammonium, aluminum,zinc, calcium and magnesium salts) of any of these compounds.

Certain very valuable mixtures of the invention are further illustratedby: a composition wherein the composition of matter includes:

one or more branched carboxylic acid of (b) and one or more branchedcarboxylic acid of (c) and one or more branched carboxylic acid of (i),optionally complemented by one or more branched carboxylic acid of (a);

one or more compounds branched carboxylic acid of (b), (d), (g) and (h)aspects optionally complemented by one or more branched carboxylic acidof (a);

one or more branched carboxylic acid of (b), (c), (d), (g) and (h)aspects optionally complemented by one or more branched carboxylic acidof (a); and

one or more branched carboxylic acid of (b), (c), (d), (g), (h) and (i)aspects optionally complemented by one or more branched carboxylic acidof (a).

Other mixture-type compositions can include only different compounds ofa single group of branched carboxylic acids, such as a mixture ofbranched carboxylic acids of (j); or any mixture in any proportions ofany branched carboxylic acid of any of the branched carboxylic acids of(a)-(k) with any known branched fatty acids, whether saturated orunsaturated, including isostearic acid, isopalmitic acid or theirunsaturated analogs.

Also encompassed by way of mixtures is a composition comprising (i) atleast about 1% of the composition of matter of any one or more of thebranched carboxylic acids (a)-(k) in said salt form; and (iii) at leastabout 1% of conventional fatty acids in salt form.

In terms of preferred composition of matter, there are also includedherein any of the composition of matter being substantially free (theterm generally meaning about 0.2% or less, or only adventitious amounts)of quaternary-carbon containing fatty acids or their salts orderivatives. Such materials reduce biodegradability of the compositions.

Another preferred composition comprises a mixture of the composition ofmatter of any one or more of the branched carboxylic acids (a)-(k) inwhich there are present at least some of the branched carboxylic acidswhich have an odd total number of carbon atoms, and at least some of thebranched carboxylic acids having an even total number of carbon atoms.

In terms of the range in total carbon atoms in the composition ofmatter, the invention preferably encompasses a composition a mixture ofthe branched carboxylic acids (a)-(k), each of the branched carboxylicacids having a total of from 12 carbon atoms to 20 carbon atoms, morepreferably from 14 carbon atoms to 19 carbon atoms, even more preferablyfrom 15 carbon atoms to 18 carbon atoms.

Another preferred composition of the invention is based on any of thebranched carboxylic acids (a)-(k), alone or in mixtures withconventional fatty acid derivatives and comprising a mixture of thecompounds, the mixture containing not more than about 0.1% by weight ofcompounds having 12 or fewer, preferably not more than about 14 orfewer, carbon atoms.

Yet another preferred composition is a mixture of the composition ofmatter(or mixtures thereof with conventional fatty acids or derivatives)wherein any alkyl substituent in any of said compounds is methyl.

Another preferred composition of the invention is based on any of thebranched carboxylic acids (a)-(k), in combination with conventionaladditives to form cleaning compositions, skin care compositions andpersonal cleansing compositions. The cleaning composition wouldcomprise:

(i) from about 0.05% to about 99.9%, preferably 0.5% to about 95%, morepreferably 1% to about 90%, even more preferably 5% to about 75% byweight of a composition of mater, namely any of the branched carboxylicacids (a)-(k), alone or in mixtures; and

(ii) from about 0.0001 to about 99.99%, preferably 0.5% to about 95%,more preferably 1% to about 90%, even more preferably 5% to about 80% byweight of conventional cleaning additive.

The skin care composition would comprise:

(i) from about 0.05% to about 99.9%, preferably 0.5% to about 95%, morepreferably 1% to about 90%, even more preferably 5% to about ₇₅% byweight of a composition of mater namely any of the branched carboxylicacids (a)-(k), alone or in mixtures; and

(ii) from about 0.0001 to about 99.99%, preferably 0.5% to about 95%,more preferably 1% to about 90%, even more preferably 5% to about 75% byweight of a conventional skin care additive.

The personal cleansing composition would comprise:

(i) from about 0.05% to about 99.9%, preferably 0.5% to about 95%, morepreferably 1% to about 90%, even more preferably 5% to about 75% byweight of a composition of mater namely any of the branched carboxylicacids (a)-(k), alone or in mixtures; and

(ii) from about 0.0001 to about 99.99%, preferably 0.5% to about 95%,more preferably 1% to about 90%, even more preferably 5% to about 75% byweight of a conventional personal cleansing additive.

Another preferred composition of the invention is paper articlecomprising at least about 0.0001% by weight of said composition ofmatter namely any of the branched carboxylic acids (a)-(k), alone or inmixtures. The paper article can be any conventional paper article wellknown in the art. This paper article can be in the form of a toilettissue, a disposable tissue or disposable wipe.

It is also preferred that the composition of mater namely any of thebranched carboxylic acids (a)-(k), alone or in mixtures comprise no morethan about 0.1% aldehyde impurity. Furthermore, it is preferred that thecomposition of mater namely any of the branched carboxylic acids(a)-(k), alone or in mixtures comprise no more than about 0.1%unsaturated impurity.

It is also preferred that composition of mater namely any of thebranched carboxylic acids (a)-(k), alone or in mixtures has at least10%, more preferably of the branched carboxylic acid has from 16 to 17carbon atoms in total. It is also preferred that the composition ofmater namely any of the branched carboxylic acids (a)-(k), alone or inmixtures comprises a mixture of at least six, more preferably 20, evenmore preferably 40, of the branched carboxylic acid.

The fabric softening compositions described hereinbefore can optionally,but preferably comprise less than about 40%, preferably from about 10%to about 35%, more preferably from about 12% to about 25%, and even morepreferably from about 14% to about 20%, of the principal solvent, byweight of the composition. Said principal solvent is selected tominimize solvent odor impact in the composition and to provide a lowviscosity to the final composition.

The suitability of any principal solvent for the formulation of theliquid, concentrated, preferably clear, fabric softener compositionsherein with the requisite stability is surprisingly selective. Suitablesolvents can be selected based upon their octanol/water partitioncoefficient (P). Octanol/water partition coefficient of a principalsolvent is the ratio between its equilibrium concentration in octanoland in water. The partition coefficients of the principal solventingredients of this invention are conveniently given in the form oftheir logarithm to the base 10, logP.

The logP of many ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Information Systems,Inc. (Daylight CIS), Irvine, Calif., contains many, along with citationsto the original literature. However, the logP values are mostconveniently calculated by the “CLOGP” program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The “calculated logP” (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each ingredient, and takes into account thenumbers and types of atoms, the atom connectivity, and chemical bonding.These ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are preferably used insteadof the experimental logP values in the selection of the principalsolvent ingredients which are useful in the present invention. Othermethods that can be used to compute ClogP include, e.g., Crippen'sfragnmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21(1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf.Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J.Med. Chem.—Chim. Theor., 19, 71 (1984). The principal solvents hereinare selected from those having a ClogP of from about 0.15 to about 0.64,preferably from about 0.25 to about 0.62, and more preferably from about0.40 to about 0.60, said principal solvent preferably being at leastsomewhat asymmetric, and preferably having a melting, or solidification,point that allows it to be liquid at, or near room temperature. Solventsthat have a low molecular weight and are biodegradable are alsodesirable for some purposes. The more asymmetric solvents appear to bevery desirable, whereas the highly symmetrical solvents such as1,7-heptanediol, or 1,4-bis(hydroxymethyl)cyclohexane, which have acenter of symmetry, appear to be unable to provide the essential clearcompositions when used alone, even though their ClogP values fall in thepreferred range.

The most preferred principal solvents can be identified by theappearance of the softener vesicles, as observed via cryogenic electronmicroscopy of the compositions that have been diluted to theconcentration used in the rinse. These dilute compositions appear tohave dispersions of fabric softener that exhibit a more unilamellarappearance than conventional fabric softener compositions. The closer touni-lamellar the appearance, the better the compositions seem toperform. These compositions provide surprisingly good fabric softeningas compared to similar compositions prepared in the conventional waywith the same fabric softener active. The compositions also inherentlyprovide improved perfume deposition as compared to conventional fabricsoftening compositions, especially when the perfume is added to thecompositions at, or near, room temperature.

A comprehensive list of possible principal solvents can be found in U.S.Pat. No. 5,747,443, which is incorporated herein by reference.

The above fabric softeners can also be combined with other fabricsofteners, such as, those in U.S. Pat. No. 3,861,870, Edwards and Diehl;U.S. Pat. No. 4,308,151, Cambre; U.S. Pat. No. 3,886,075, Bernardino;U.S. Pat. No. 4,233,164, Davis; U.S. Pat. No. 4,401,578, Verbruggen;U.S. Pat. No. 3,974,076, Wiersema and Rieke; and U.S. Pat. No.4,237,016, Rudkin, Clint, and Young, all of said patents beingincorporated herein by reference. The additional softener actives hereinare preferably those that are highly branched and/or unsaturatedversions of the traditional softener actives, i.e., di-long chain alkylnitrogen derivatives, normally cationic materials, such asdioleyldimethylammonium chloride and imidazolinium compounds asdescribed hereinafter. Examples of more biodegradable fabric softenerscan be found in U.S. Pat. No. 3,408,361, Mannheimer, issued Oct. 29,1968; U.S. Pat. No. 4,709,045, Kubo et al., issued Nov. 24, 1987; U.S.Pat. No. 4,233,451, Pracht et al., issued Nov. 11, 1980; U.S. Pat. No.4,127,489, Pracht et al., issued Nov. 28, 1979; U.S. Pat. No. 3,689,424,Berg et al., issued Sep. 5, 1972; U.S. Pat. No. 4,128,485, Baumann etal., issued Dec. 5, 1978; U.S. Pat. No. 4,161,604, Elster et al., issuedJul. 17, 1979; U.S. Pat. No. 4,189,593, Wechsler et al., issued Feb. 19,1980; and U.S. Pat. No. 4,339,391, Hoffman et al., issued Jul. 13, 1982,said patents being incorporated herein by reference.

An example of Compound 4, is1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methylsulfate wherein R¹is as defined above, R² is an ethylene group, G is a NH group, R⁵ is amethyl group and X⁻ is a methyl sulfate anion.

An example of Compound 5, is 1-oleylamidoethyl-2-oleylimidazolinewherein R¹ is as defined above, R² is an ethylene group, and G is a NHgroup.

An example of Compound 6, is reaction products of oleic acids withdiethylenetriamine in a molecular ratio of about 2:1, said reactionproduct mixture containing N,N″-dioleoyldiethylenetriamine with theformula:

R¹—C(O)—NH—CH₂CH₂—NH—CH₂CH₂—NH—C(O)—R¹

wherein R¹—C(O) is oleoyl group of any of the novel branched acidsdescribed herein or any commercially available oleic acid derived from avegetable or animal source, such as Emersol® 223LL or Emersol® 7021,available from Henkel Corporation, and R² and R³ are divalent ethylenegroups.

An example of Compound 7, is a difatty amidoamine based softener havingthe formula:

[R¹—C(O)—NH—CH₂CH₂—N(CH₃)(CH₂CH₂OH)—CH₂CH₂—NH—C(O)—R¹]⁺CH₃SO₄—

wherein R¹—C(O) is oleoyl group of any of the novel branched acidsdescribed herein or any commercially available oleic acid derived from avegetable or animal source.

An example of Compound 8, is reaction products of oleic acids withN-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1, saidreaction product mixture containing a compound of the formula:

R¹—C(O)—NH—CH₂CH₂—N(CH₂CH₂OH)—C(O)—R¹

wherein R¹—C(O) is oleoyl group of any of the novel branched acidsdescribed herein or any commercially available oleic acid derived from avegetable or animal source such as Emersol® 223LL or Emersol® 7021,available from Henkel Corporation.

An example of Compound 9, is the diquatemary compound having theformula:

wherein R¹ is oleoyl group of any of the novel branched acids describedherein.

An example of Compound 13, is1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfatewherein R¹ is as defined above, R² is an ethylene group, R⁵ is an ethylgroup, and X⁻ is an ethylsulfate anion.

The invention has numerous additional useful embodiments as describedand illustrated in the examples, detergent examples and claimshereinafter.

EXAMPLE 1 5-Methylpentadecanoic Acid

See GENERAL PROCEDURE I. Decyl bromide (compound (1), R═CH₃(CH₂)₉—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4). (4) is converted to its Grignardreagent following standard practice. (I, Step (e)). The Grignard reagentis treated with carbon dioxide and aqueous acidic workup (I, Step (f))followed by catalytic hydrogenation (Pd catalyst) to form5-methylpentadecanoic acid, (5).

EXAMPLE 2 7-Methyltridecanoic Acid

See GENERAL PROCEDURE I. Hexyl bromide (compound (1), R═CH₃(CH₂)₅—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₅—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with ethylene oxide followed by aqueousacidic workup (I, Step (h)), hydrogenation (I, Step (i)), Pd catalyst,and hydrobromination (I, Step (j)). The alkyl bromide (6) (R═CH₃(CH₂)₅—,y=5) is converted to the Grignard reagent with magnesium (1, Step (k)),which is treated with carbon dioxide and aqueous acidic workup (I, Step(1)) to give the product, 7-methyltridecanoic acid, (7).

EXAMPLE 3 8-Methylpentadecanoic Acid

See GENERAL PROCEDURE I. Heptyl bromide (compound (1), R═CH₃(CH₂)₆—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₆—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with ethylene oxide followed by aqueousacidic workup (1, Step (h)), hydrogenation (I, Step (i)), Pd catalyst,and hydrobromination (I, Step (j)). The alkyl bromide (6) (R═CH₃(CH₂)₆—,y=5) is converted to the Grignard reagent with magnesium (I, Step (k)),which is treated with formaldehyde, and aqueous workup (I, Step (m).Alkyl halide (8) (R═CH₃(CH₂)₆—, x=6) is formed by hydrobromination (I,Step (o)). This is converted to its Grignard reagent with magnesium indry ether (1, Step (p)) followed by treatment with carbon dioxide andaqueous acidic workup (I, Step (q)) to give the product,8-methylpentadecanoic acid, (9).

EXAMPLE 4 9-Methylpentadecanoic Acid

See GENERAL PROCEDURE I. Hexyl bromide (compound (1), R═CH₃(CH₂)₅—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₅—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with ethylene oxide followed by aqueousacidic workup (I, Step (h)), hydrogenation (I, Step (i)), Pd catalyst,and hydrobromination (I, Step (j)). The alkyl bromide (6) (R═CH₃(CH₂)₅—,y=5) is converted to the Grignard reagent with magnesium (I, Step (k))which is treated with ethylene oxide and aqueous acidic workup (I, Step(h)) and hydrobromination (I, Step (j)). The alkyl bromide (6)(R═CH₃(CH₂)₅—, y=7) is converted to the Grignard reagent with magnesium(I, Step (k)) which is treated with carbon dioxide and aqueous acidicworkup (I, Step (I)) to give the product, 9-methylpentadecanoic acid,(7).

EXAMPLE 5 10-Methyltridecanoic Acid

See GENERAL PROCEDURE I. 1-propyl bromide (compound (1), R═CH₃(CH₂)₂—)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₂—). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with ethylene oxide followed byaqueous acidic workup (I, Step (h)), hydrogenation (1, Step (i)), Pdcatalyst, and hydrobromination (I, Step (j)). The alkyl bromide (6)(R═CH₃(CH₂)₂—, y=5) is converted to the Grignard reagent with magnesium(I, Step (k)). Departing from General Procedure I, this Grignard reagentis again treated with ethylene oxide followed by aqueous acidic workupand hydrobromination. The intermediate alkyl bromide,CH₃(CH₂)₂CH(Me)(CH₂)₇Br, is converted to the Grignard reagent withmagnesium, which, returning to the general procedure I at step (I m), istreated with formaldehyde, and aqueous workup (I, Step (m). Alkyl halide(8) (R═CH₃(CH₂)₂—, x=8) is formed by hydrobromination (I, Step (o)).This is converted to its Grignard reagent with magnesium in dry ether(I, Step (p)) followed by treatment with carbon dioxide and aqueousacidic workup (I, Step (q)) to give the product, 10-methyltridecanoicacid, (9).

EXAMPLE 6 6-Propyltetradecanoic Acid

Following General Procedure VIII use 1-bromopropane in step (c)(Z═CH₃(CH₂)₂—) and use 1-bromohexane in step (f) (R═CH₃(CH₂)₅—) toeventually obtain 2-propyl-1-decanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-2), (o), (p) (that is, oneethylene oxide iteration and one formaldehyde iteration) gives finalGrignard reagent (12), x=4, R═n-hexyl, Z=n-Pr which with CO₂ treatmentgives 6-propyltetradecanoic acid (13) (x=4, R═n-hexyl, Z=n-Pr).

EXAMPLE 7 8-Ethylpentadecanoic Acid

Following General Procedure VIII use ethyl bromide in step (c)(Z═CH₃CH₂—) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄—) toeventually obtain 2-ethyl-1-nonanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-1), (o), (p), (n-2), (o), (p)(that is, two ethylene oxide iterations and one formaldehyde iteration)gives final Grignard reagent (12), x=6, R═n-pentyl, Z=Et which with CO₂treatment gives 8-ethylpentadecanoic acid (13) (x=6, R═n-pentyl, Z=Et).

EXAMPLE 8 6-Methyltridecanoic Acid

See GENERAL PROCEDURE I. Heptyl bromide (compound (1), R═CH₃(CH₂)₆—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₆—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). This istreated with formaldehyde step and aqueous workup (I m), hydrogenation(I n). Alkyl halide (8) (R═CH₃(CH₂)₆—, x=4) is formed byhydrobromination (I, Step (o)). This is converted to its Grignardreagent with magnesium in dry ether (I, Step (p)) followed by treatmentwith carbon dioxide and aqueous acidic workup (I, Step (q)) to give theproduct, 6-methyltridecanoic acid, (9).

EXAMPLE 9 2,5-Dimethyltetradecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

A Grignard reagent is made from 2-bromoundecane and magnesium (II, step(f)) which is treated (II, step (g)) with cadmium chloride to form thecorresponding dialkylcadmium, di(2-undecyl)cadmium, (5).

The dialkylcadmium reagent (5) is allowed to react with the acidchloride compound (4) (II, step (h)) to form (6) (R=2-undecyl). This ishydrolyzed to the corresponding keto-acid (7) which is reduced eitherwith the Wolff-Kishner or Clemmensen reductions II, step (j)) to give2,5-dimethyltetradecanoic acid.

EXAMPLE 10 2,7-Dimethyltetradecanoic Acid

The compound is prepared from 2-nonyl bromide (1) and succinic anhydrideusing Procedure III. y=2.

EXAMPLE 11 2,9-Dimethyltetradecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

Now see GENERAL PROCEDURE I. 1-pentyl bromide (compound (1),R═CH₃(CH₂)₄—) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(R═CH₃(CH₂)₄—). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withformaldehyde and aqueous workup (I, Step (m)) and hydrogenated (I, Step(n)), Pd catalyst, and hydrobrominated (I, Step (o)) to give the alkylbromide (8) (R═CH₃(CH₂)₄—, x=4). Now this compound (8) of Procedure I iscarried over and used following part of the procedure shown in GENERALPROCEDURE II, as an alkyl halide and is converted to the Grignardreagent with magnesium (II, Step (f)). The Grignard reagent is convertedto a dialkylcadmium (5), di(5-methyl-1-decyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-decyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,9-dimethyltetradecanoic acid.

EXAMPLE 12 2,11-Dimethyltetradecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

Now see GENERAL PROCEDURE I. 1-propyl bromide (compound (1),R═CH₃(CH₂)₂—) is converted to its Grignard reagent with magnesium in dryether (I, Step (a)). To this is added 5-chloro-2-pentanone (AldrichC6,2660-3) (I, Step (b)). The reaction mixture is worked up with aceticanhydride (I, Step (c)) to form chloroacetate (3). Acetic acid iseliminated by refluxing (3) in a suitable solvent, e.g., benzene (I,Step (d)) yielding a mixture of chloro-olefin isomers (4)(P═CH₃(CH₂)₂—). (4) is converted to its Grignard reagent followingstandard practice. (I, Step (e)). The Grignard reagent is treated withformaldehyde and aqueous workup (I, Step (m)) and hydrogenated (I, Step(n)), Pd catalyst, and hydrobrominated (I, Step (o)) to give the alkylbromide (8) (R═CH₃(CH₂)₂—, x=4). Now following another part of theprocedure shown in GENERAL PROCEDURE I, compound (8) is used instead ofcompound (4) of Procedure I as an alkyl halide and is converted to aGrignard reagent with magnesium (I, Step (e)). The Grignard reagent istreated with ethylene oxide followed by aqueous acidic workup (I, Step(h)), and hydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-decyl, y=6), Now this compound (6) is used in another partof the procedure shown in GENERAL PROCEDURE II, namely, step (II, (f))where it is converted to a Grignard reagent, The Grignard reagent isconverted to a dialkylcadmium (5), di(7-methyl-1-decyl)cadmium (II,(g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-decyl-. This is hydrolyzed tothe corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step t)) to give2,11-dimethyltetradecanoic acid.

EXAMPLE 13 2,13-Dimethyltetradecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

Now see GENERAL PROCEDURE I. Methyl iodide (compound (1)) is convertedto its Grignard reagent with magnesium in dry ether (I, Step (a)). Tothis is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step (b)).The reaction mixture is worked up with acetic anhydride (I, Step (c)) toform chloroacetate (3). Acetic acid is eliminated by refluxing (3) in asuitable solvent, e.g., benzene (I, Step (d)) yielding a mixture ofchloro-olefin isomers (4) (R═CH₃—). (4) is converted to its Grignardreagent following standard practice. (I, Step (e)). The Grignard reagentis treated with formaldehyde and aqueous workup (I, Step (m)) andhydrogenated (I, Step (n)), Pd catalyst, and hydrobrominated (I, Step(o)) to give the alkyl bromide (8) (R═CH₃—, x=4). Now following anotherpart of the procedure shown in GENERAL PROCEDURE I, compound (8) is usedinstead of compound (4) of Procedure I as an alkyl halide and isconverted to a Grignard reagent with magnesium, (I, Step (e)). TheGrignard reagent is treated with ethylene oxide followed by aqueousacidic workup (I, Step (h)), and hydrobromination (I, Step (j)), to givecompound (6) (R=Methyl, y=6). In a second Grignard/ethylene oxide loop,compound (6) is converted to its Grignard reagent, treated with ethyleneoxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give a new compound (6) (R=Methyl,y=8).

Now this compound (6) is used in another part of the procedure shown inGENERAL PROCEDURE II, namely, step (II, (f)) where it is converted to aGrignard reagent. The Grignard reagent is converted to a dialkylcadmium(5), di(9-methyl-1-decyl)cadmium (II, (g)). The dialkylcadmium isreacted (II, step (h)) with the acid chloride of 2-methylsuccinic acid1-methyl ester (compound (4) prepared supra) yielding compound (6),R=9-methyl-1-decyl-. This is hydrolyzed to the corresponding keto-acid(7) which is reduced either with the Wolff-Kishner or Clemmensenreductions (II, step (j)) to give 2,13-dimethyltetradecanoic acid.

EXAMPLE 14 2,15-Dimethylhexadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

Now see GENERAL PROCEDURE I. Methyl iodide (compound (1)) is convertedto its Grignard reagent with magnesium in dry ether (I, Step (a)). Tothis is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step (b)).The reaction mixture is worked up with acetic anhydride (I, Step (c)) toform chloroacetate (3). Acetic acid is eliminated by refluxing (3) in asuitable solvent, e.g., benzene (I, Step (d)) yielding a mixture ofchloro-olefin isomers (4) (R═CH₃—). (4) is converted to its Grignardreagent following standard practice. (I, Step (e)). The Grignard reagentis treated with formaldehyde and aqueous workup (I, Step (m)) andhydrogenated (I, Step (n)), Pd catalyst, and hydrobrominated (I, Step(o)) to give the alkyl bromide (8) (R═CH₃—, x=4). Now following anotherpart of the procedure shown in GENERAL PROCEDURE I, compound (8) is usedinstead of compound (4) of Procedure I as an alkyl halide and isconverted to a Grignard reagent with magnesium (I, Step (e)). TheGrignard reagent is treated with ethylene oxide followed by aqueousacidic workup (I, Step (h)), and hydrobromination (I, Step (j)), to givecompound (6) (R=Methyl, y=6). In two additional Grignard/ethylene oxideloops, compound (6) is converted to Grignard reagent, treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), ultimately giving compound (6)(R=Methyl, y=10). Now this compound (6) is used in another part of theprocedure shown in GENERAL PROCEDURE II, namely, step (II, (f)) where itis converted to a Grignard reagent. The Grignard reagent is converted toa dialkylcadmium (5), di(11-methyl-1-dodecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=11-methyl-1-dodecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,15-dimethylhexadecanoic acid.

EXAMPLE 15 2,17-Dimethyloctadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4).

Now see GENERAL PROCEDURE I. Methyl bromide (compound (1)) is convertedto its Grignard reagent with magnesium in dry ether (I, Step (a)). Tothis is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step (b)).The reaction mixture is worked up with acetic anhydride (I, Step (c)) toform chloroacetate (3). Acetic acid is eliminated by refluxing (3) in asuitable solvent, e.g., benzene (I, Step (d)) yielding a mixture ofchloro-olefin isomers (4) (R═CH₃—). (4) is converted to its Grignardreagent following standard practice. (I, Step (e)). The Grignard reagentis treated with formaldehyde and aqueous workup (I, Step (m)) andhydrogenated (I, Step (n)), Pd catalyst, and hydrobrominated (I, Step(o)) to give the alkyl bromide (8) (R═CH₃—, x=4). Now following anotherpart of the procedure shown in GENERAL PROCEDURE I, compound (8) is usedinstead of compound (4) of Procedure I as an alkyl halide and isconverted to a Grignard reagent with magnesium (I, Step (e)). TheGrignard reagent is treated with ethylene oxide followed by aqueousacidic workup (I, Step (h)), and hydrobromination (I, Step (j)), to givecompound (6) (R=Methyl, y=6). In three Grignard/ethylene oxide loops,compound (6) is converted to Grignard reagent, treated with ethyleneoxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), ultimately giving compound (6)(R=Methyl, y=12). Now this compound (6) is used in another part of theprocedure shown in GENERAL PROCEDURE II, namely, step (II, (f)) where itis converted to a Grignard reagent. The Grignard reagent is converted toa dialkylcadmium (5), R═di(13-methyl-1-tetradecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=13-methyl-1-tetradecyl-. This is hydrolyzed tothe corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,17-dimethyloctadecanoic acid.

EXAMPLE 16 2,5-Dimethylpentadecanoic Acid

The compound is made using the following variations with respect toExample 9:

The alkyl halide is 2-bromododecane in replacement for 2-bromoundecanein Example 9. The Cd intermediate is di(2-dodecyl)cadmium. The productis 2,5-dimethylpentadecanoic acid.

EXAMPLE 17 2,5-Dimethylhexadecanoic Acid

The compound is made using the following variations with respect toExample 9:

The alkyl halide is 2-bromotridecane in replacement for 2-bromoundecanein Example 9. The Cd intermediate is di(2-tridecyl)cadmium. The productis 2,5-dimethylhexadecanoic acid.

EXAMPLE 18 2,5-Dimethyloctadecanoic Acid

The compound is made using the following variations with respect toExample 9:

The alkyl halide is 2-bromopentadecane in replacement for2-bromoundecane in Example 9. The Cd intermediate isdi(2-pentadecyl)cadmium. The product is 2,5-dimethyloctadecanoic acid.

EXAMPLE 19 2,7-Dimethylpentadecanoic Acid

The compound is made using the following variations with respect toExample 10:

The alkyl halide is 2-bromodecane. y=2.

EXAMPLE 20 2,7-Dimethylhexadecanoic Acid

The compound is made using the following variations with respect toExample 10:

The alkyl halide is 2-bromoundecane. y=2.

EXAMPLE 21 2,7-Dimethylheptadecanoic Acid

The compound is made using the following variations with respect toExample 10:

The alkyl halide is 2-bromododecane. y=2.

EXAMPLE 22 2,7-Dimethyloctadecanoic Acid

The compound is made using the following variations with respect toExample 10:

The alkyl halide is 2-bromotridecane. y=2.

EXAMPLE 23 2,9-Dimethylpentadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE 1. 1-hexyl bromide (compound (1), R═CH₃(CH₂)₅—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₅—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₅—, x=4). Now this compound (8) of Procedure I is carriedover and used following part of the procedure shown in GENERAL PROCEDUREII, as an alkyl halide and is converted to the Grignard reagent withmagnesium (II, Step (f)). The Grignard reagent is converted to adialkylcadmium (5), di(5-methyl-1-undecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-undecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,9-Dimethylpentadecanoic acid.

EXAMPLE 24 2,9-Dimethylhexadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE 1. 1-heptyl bromide (compound (1), R═CH₃(CH₂)₆—)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₆—). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I,. Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₆—, x=4). Now this compound (8) of Procedure I is carriedover and used following part of the procedure shown in GENERAL PROCEDUREII, as an alkyl halide and is converted to the Grignard reagent withmagnesium (II, Step (f)). The Grignard reagent is converted to adialkylcadmium (5), di(5-methyl-1-dodecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-dodecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,9-Dimethylhexadecanoic acid.

EXAMPLE 25 2,9-Dimethylheptadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-octyl bromide (compound (1), R═CH₃(CH₂)₇—))is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₇—). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₇—, x=4). Now this compound (8) of Procedure I is carriedover and used following part of the procedure shown in GENERAL PROCEDUREII, as an alkyl halide and is converted to the Grignard reagent withmagnesium (II, Step (f)). The Grignard reagent is converted to adialkylcadmium (5), di(5-methyl-1-tridecyl)cadmium (II, (g)). Thedialkylcadmium is reacted (II, step (h)) with the acid chloride of2-methylsuccinic acid 1-methyl ester (compound (4) prepared supra)yielding compound (6), R=5-methyl-1-tridecyl-. This is hydrolyzed to thecorresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,9-dimethyltetradecanoic acid.

EXAMPLE 26 2,11-Dimethylpentadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-butyl bromide (compound (1), R═CH₃(CH₂)₃—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₃—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₃—, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-undecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-undecyl)cadmium (II,(g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-undecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethylpentadecanoic acid.

EXAMPLE 27 2,11-Dimethylhexadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-pentyl bromide (compound (1), R═CH₃(CH₂)₄—)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (1,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₄—). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₄—, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-dodecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-dodecyl)cadmium (II,(g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-dodecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step (6)) to give2,11-dimethylhexadecanoic acid.

EXAMPLE 28 2,11-Dimethylheptadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE 1. 1-hexyl bromide (compound (1), R═CH₃(CH₂)₅—) isconverted to its Grignard reagent with magnesium in dry ether (I, Step(a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I, Step(b)). The reaction mixture is worked up with acetic anhydride (I, Step(c)) to form chloroacetate (3). Acetic acid is eliminated by refluxing(3) in a suitable solvent, e.g., benzene (I, Step (d)) yielding amixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₅—). (4) is converted toits Grignard reagent following standard practice. (I, Step (e)). TheGrignard reagent is treated with formaldehyde and aqueous workup (I,Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₅—, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-tridecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-tridecyl)cadmium(II, (g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-tridecyl-. This is hydrolyzedto the corresponding keto-acid (7) which is reduced either with theWolff-Kishner or Clemmensen reductions (II, step ()) to give2,11-dimethylheptadecanoic acid.

EXAMPLE 29 2,11-Dimethyloctadecanoic Acid

Succinic anhydride is opened using methanol (II, step (a)) to givemonomethyl succinate (2). This is treated with 2+ equivalents of lithiumamide in liquid ammonia (II, step (b)) to form its dianion which isalkylated by the addition of one mole of methyl iodide in ether (II,step (c)) and treatment with ammonium chloride (II, step (d)), giving2-methylsuccinic acid, 1-methyl ester (3). This is treated with thionylchloride (II, step (e)) to give the corresponding acid chloride (4). Nowsee GENERAL PROCEDURE I. 1-heptyl bromide (compound (1), R═CH₃(CH₂)₆—)is converted to its Grignard reagent with magnesium in dry ether (I,Step (a)). To this is added 5-chloro-2-pentanone (Aldrich C6,2660-3) (I,Step (b)). The reaction mixture is worked up with acetic anhydride (I,Step (c)) to form chloroacetate (3). Acetic acid is eliminated byrefluxing (3) in a suitable solvent, e.g., benzene (I, Step (d))yielding a mixture of chloro-olefin isomers (4) (R═CH₃(CH₂)₆—). (4) isconverted to its Grignard reagent following standard practice. (I, Step(e)). The Grignard reagent is treated with formaldehyde and aqueousworkup (I, Step (m)) and hydrogenated (I, Step (n)), Pd catalyst, andhydrobrominated (I, Step (o)) to give the alkyl bromide (8)(R═CH₃(CH₂)₆—, x=4). Now following another part of the procedure shownin GENERAL PROCEDURE I, compound (8) is used instead of compound (4) ofProcedure I as an alkyl halide and is converted to the Grignard reagentwith magnesium (I, Step (e)). The Grignard reagent is treated withethylene oxide followed by aqueous acidic workup (I, Step (h)), andhydrobromination (I, Step (j)), to give compound (6)(R=7-methyl-1-tetradecyl, y=6). Now this compound (6) is used in anotherpart of the procedure shown in GENERAL PROCEDURE II, namely, step (II,(f)) where it is converted to a Grignard reagent. The Grignard reagentis converted to a dialkylcadmium (5), di(7-methyl-1-tetradecyl)cadmium(II, (g)). The dialkylcadmium is reacted (II, step (h)) with the acidchloride of 2-methylsuccinic acid 1-methyl ester (compound (4) preparedsupra) yielding compound (6), R=7-methyl-1-tetradecyl-. This ishydrolyzed to the corresponding keto-acid (7) which is reduced eitherwith the Wolff-Kishner or Clemmensen reductions (II, step (j)) to give2,11-dimethyloctadecanoic acid.

EXAMPLE 30 2,13-Dimethylpentadecanoic Acid

The procedure is as described in Example 13 except that Ethyl Bromidereplaces Methyl iodide in Step Ia.

EXAMPLE 31 2,13-Dimethylhexadecanoic Acid

The procedure is as described in Example 13 except that 1-propyl Bromidereplaces Methyl iodide in Step Ia.

EXAMPLE 32 2,13-Dimethylheptadecanoic Acid

The procedure is as described in Example 13 except that 1-butyl Bromidereplaces Methyl iodide in Step Ia.

EXAMPLE 33 2,13-Dimethyloctadecanoic Acid

The procedure is as described in Example 13 except that 1-pentyl Bromidereplaces Methyl iodide in Step Ia.

EXAMPLE 34 2,15-Dimethylheptadecanoic Acid

The procedure is as described in Example 14 except that Ethyl Bromidereplaces Methyl iodide in Step Ia.

EXAMPLE 35 2,15-Dimethyloctadecanoic Acid

The procedure is as described in Example 14 except that 1-propyl Bromidereplaces Methyl iodide in Step Ia.

EXAMPLE 36 2-Ethyl-5-methyltetradecanoic Acid

The procedure is as described in Example 9 except that Ethyl Bromidereplaces Methyl Iodide.

EXAMPLE 37 2-Ethyl-7-methyltetradecanoic Acid The procedure is asdescribed in Example 10 except that Ethyl Bromide replaces Methyl Iodidein step (h). EXAMPLE 38 2-Ethyl-9-methyltetradecanoic Acid

The procedure is as described in Example 11 except that Ethyl Bromidereplaces Methyl Iodide.

EXAMPLE 39 2-Ethyl-11-methyltetradecanoic Acid

The procedure is as described in Example 12 except that Ethyl Bromidereplaces Methyl Iodide.

EXAMPLE 40 2-Ethyl-13-methyltetradecanoic Acid

The procedure is as described in Example 13 except that Ethyl Bromidereplaces Methyl Iodide.

EXAMPLE 41 2-Ethyl-5-methyltridecanoic Acid

The procedure is as described in Example 9 except that Ethyl Bromidereplaces Methyl Iodide and 2-bromodecane replaces 2-bromoundecane.

EXAMPLE 42 2-Ethyl-7-methyltridecanoic Acid

The procedure is as described in Example 10 except that Ethyl Bromidereplaces Methyl Iodide in step (h) and 2-octyl bromide replaces 2-nonylbromide.

EXAMPLE 43 2-Ethyl-9-methyltridecanoic Acid

The procedure is as described in Example 11 except that Ethyl Bromidereplaces Methyl Iodide and 1-bromobutane replaces 1-pentyl bromide.

EXAMPLE 44 2-Ethyl-11-methyltridecanoic Acid

The procedure is as described in Example 12 except that Ethyl Bromidereplaces Methyl Iodide in procedure II step (c) and ethyl bromide alsoreplaces 1-propyl bromide in procedure I step (a).

EXAMPLE 45 2-Ethyl-6-methyltetradecanoic Acid

The procedure used is that of GENERAL PROCEDURE III except that2-bromodecane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and ethyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 46 2-Ethyl-6-methyltridecanoic Acid

The procedure used is that of GENERAL PROCEDURE III except that2-bromononane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and ethyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 47 2-Ethyl-8-methyltetradecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=5, k=1.

EXAMPLE 48 2-Ethyl-8-methyltridecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=4, k=1.

EXAMPLE 49 2-ethyl-10-methyltetradecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=3, k=2.

EXAMPLE 50 7,8-Dimethyltridecanoic Acid

The procedure used is that of GENERAL PROCEDURE V. x=4, y=2.

EXAMPLE 51 7,8-Dimethylpentadecanoic Acid

The procedure used is that of GENERAL PROCEDURE V. x=6, y=2.

EXAMPLE 52 9,10-Dimethylpentadecanoic Acid

The procedure used is that of GENERAL PROCEDURE V. x=4, y=4.

EXAMPLE 53 9,10-Dimethylheptadecanoic Acid

The procedure used is that of GENERAL PROCEDURE V. x=6, y=4.

EXAMPLE 54 8,9-Dimethylpentadecanoic Acid

The procedure used is that of GENERAL PROCEDURE VI. x=5, y=3.

EXAMPLE 55 2-Propyl-5-methyltridecanoic Acid

The procedure is as described in Example 9 except that Propyl Bromidereplaces Methyl Iodide and 2-bromodecane replaces 2-bromoundecane.

EXAMPLE 56 2-Propyl-7-methyltridecanoic Acid

The procedure is as described in Example 10 except that Propyl Bromidereplaces Methyl Iodide and 2-Bromooctane replaces 2-bromononane. y=2.

EXAMPLE 57 2-Propyl-9-methyltridecanoic Acid

The procedure is as described in Example 11 except that Propyl Bromidereplaces Methyl Iodide in step (c) of GENERAL PROCEDURE II and 1-butylbromide replaces 1-pentyl bromide in step (a) of GENERAL PROCEDURE I.

EXAMPLE 58 2-Propyl-11-methyltridecanoic Acid

The procedure is as described in Example 12 except that Propyl Bromidereplaces Methyl Iodide in Step IIc and ethyl bromide replaces 1-propylbromide in step Ia.

EXAMPLE 59 2-Propyl-5-methyldodecanoic Acid

The procedure is as described in Example 9 except that Propyl Bromidereplaces Methyl Iodide and 2-bromononane replaces 2-bromoundecane.

EXAMPLE 60 2-Propyl-7-methyldodecanoic Acid

The procedure is as described in Example 10 except that Propyl Bromidereplaces Methyl Iodide and 2-bromoheptane replaces 2-bromononane. y=2.

EXAMPLE 61 2-Propyl-9-methyldodecanoic Acid

The procedure is as described in Example 11 except that Propyl Bromidereplaces Methyl Iodide in step IIc and 1-propyl bromide replaces1-pentyl bromide in step Ia.

EXAMPLE 62 2-Propyl-11-methyldodecanoic Acid

The procedure is as described in Example 12 except that Propyl Bromidereplaces Methyl Iodide in step IIc and methyl iodide replaces 1-propylbromide in step Ia.

EXAMPLE 63 2-Propyl-6-methyltridecanoic Acid

The procedure used is that of GENERAL PROCEDURE III except that2-bromononane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and propyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 64 2-Propyl-6-methyldodecanoic Acid

The procedure used is that of GENERAL PROCEDURE III except that2-bromooctane is used as compound (1) in step (a), formaldehyde is usedin place of ethylene oxide in step (b), y=1, and propyl bromide is usedin place of methyl iodide in step (h).

EXAMPLE 65 2-Propyl-8-methyltridecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=4, k=1 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 66 2-Propyl-8-methyldodecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=3, k=1 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 67 2-Propyl-10-methyltridecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=2, k=2 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 68 2-Propyl-10-methyldodecanoic Acid

The procedure used is that of GENERAL PROCEDURE IV. j=1, k=2 and1-propyl bromide replaces ethyl bromide.

EXAMPLE 69 6,7-Dimethylundecanoic Acid

The procedure used is that of GENERAL PROCEDURE VII starting with2-bromohexane; x=3, y=1.

EXAMPLE 70 9-Ethyltridecanoic Acid

Following General Procedure VIII use ethyl bromide in step (c)(Z═CH₃CH₂—) and use ethyl bromide in step (f) (R═CH₃CH₂—) to eventuallyobtain 2-ethyl-1-hexanol as compound (9). This is converted to itsbromide in step (1) and to its Grignard reagent in step (m). Followingthe sequence (n-1), (o), (p), (n-1), (o), (p), (n-1), (o), (p) (that is,three iterations of ethylene oxide) gives final Grignard reagent (12),x=7, R═Et, Z=Et which with CO₂ treatment gives 9-ethyltridecanoic acid(13) (x=7, R═Et, Z=Et).

EXAMPLE 71 9-Propyldodecanoic Acid

Following General Procedure VIII use 1-bromopropane in step (c)(Z═CH₃(CH₂)₂—) and use methyl bromide in step (f) (R═CH₃—) to eventuallyobtain 2-propyl-1-pentanol as compound (9). This is converted to itsbromide in step (1) and to its Grignard reagent in step (m). Followingthe sequence (n-1), (o), (p), (n-1), (o), (p), (n-1), (o), (p) (that is,three iterations of ethylene oxide) gives final Grignard reagent (12),x=7, R=Me, Z=n-Pr which with CO₂ treatment gives 9-propyldodecanoic acid(13) (x=7, R=Me, Z=n-Pr).

EXAMPLE 72 9-Ethylpentadecanoic Acid

Following General Procedure VIII use ethyl bromide in step (c)(Z═CH₃CH₂—) and use 1-bromobutane in step (f) (R═CH₃(CH₂)₃—) toeventually obtain 2-ethyl-1-octanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-1), (o), (p), (n-1), (o), (p)(that is, three iterations of ethylene oxide) gives final Grignardreagent (12), x=7, R═n-Bu, Z=Et which with CO₂ treatment gives9-ethylpentadecanoic acid (13) (x=7, R═n-Bu, Z=Et).

EXAMPLE 73 9-Propyltetradecanoic Acid

Following General Procedure VIII use 1-bromopropane in step (c)(Z═CH₃(CH₂)₂—) and use 1-bromopropane in step (f) (R═CH₃(CH₂)₂—) toeventually obtain 2-propyl-1-octanol as compound (9). This is convertedto its bromide in step (I) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-1), (o), (p), (n-1), (o), (p)(that is, three iterations of ethylene oxide) gives final Grignardreagent (12), x=7, R═n-Pr, Z=n-Pr which with CO₂ treatment gives9-propyltetradecanoic acid (13) (x=7, R═n-Pr, Z=n-Pr).

EXAMPLE 74 7-Propyltetradecanoic Acid

Following General Procedure VIII use 1-bromopropane in step (c)(Z═CH₃(CH₂)₂—) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄—) toeventually obtain 2-propyl-1-nonanol as compound (9). This is convertedto its bromide in step (I) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-1), (o), (p), (that is, twoiterations of ethylene oxide) gives final Grignard reagent (12), x=5,R═n-pentyl, Z=n-Pr which with CO₂ treatment gives 7-propyltetradecanoicacid (13) (x=5, R═n-pentyl, Z=n-Pr).

EXAMPLE 75 7-Ethylpentadecanoic Acid

Following General Procedure VIII use ethyl bromide in step (c)(Z═CH₃CH₂—) and use 1-bromohexane in step (f) (R═CH₃(CH₂)₅—) toeventually obtain 2-ethyl-1-decanol as compound (9). This is convertedto its bromide in step (I) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-1), (o), (p), (that is, twoiterations of ethylene oxide) gives final Grignard reagent (12), x=5,R═n-hexyl, Z=Et which with CO₂ treatment gives 7-ethylpentadecanoic acid(13) (x=5, R═n-hexyl, Z=Et).

EXAMPLE 76 5-Propyldodecanoic Acid

Following General Procedure VIII use 1-bromopropane in step (c)(Z═CH₃(CH₂)₂—) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄—) toeventually obtain 2-propyl-1-nonanol as compound (9). This is convertedto its bromide in step (1) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p) gives final Grignard reagent(12), x=3, R═n-pentyl, Z=n-Pr which with CO₂ treatment gives5-propyldodecanoic acid (13) (x=3, R═n-pentyl, Z=n-Pr).

EXAMPLE 77 6-Ethyltridecanoic Acid

Following General Procedure VIII use ethyl bromide in step (c)(Z═CH₃CH₂—) and use 1-bromopentane in step (f) (R═CH₃(CH₂)₄—) toeventually obtain 2-ethyl-1-nonanol as compound (9). This is convertedto its bromide in step (I) and to its Grignard reagent in step (m).Following the sequence (n-1), (o), (p), (n-2), (o), (p) (that is, oneethylene oxide iteration and one formaldehyde iteration) gives finalGrignard reagent (12), x=4, R═n-pentyl, Z=Et which with CO₂ treatmentgives 6-ethyltridecanoic acid (13) (x=4, R═n-pentyl, Z=Et).

EXAMPLE 78 Sodium Soaps

10 mmol of fatty acid is added to about 10.2 mmol of sodium hydroxidepredissolved in 100 ml of methanol. A little water may optionally bepresent. The methanol is evaporated to give the soap. The sodium soap ismade in this way for each one of the preceding fatty acids listed above.

EXAMPLE 79 Potassium Soaps

10 mmol of fatty acid is added to about 10.2 mmol of potassium hydroxidepredissolved in 100 ml of methanol. A little water may optionally bepresent. The methanol is evaporated to give the soap. The potassium soapis made in this way for each one of the preceding fatty acids listedabove.

EXAMPLE 80 Ammonium Soaps

10 mmol of fatty acid is added to about 10.2 mmol of ammonia (used asconcentrated aqueous reagent) predissolved in 100 ml of methanol. Thesolvent is evaporated to give the soap. The ammonium soap is made inthis way for each one of the preceding fatty acids listed above.

EXAMPLE 81 Calcium Soaps

Sodium Soap made as per Example 78 (10 mmol) is dissolved in water andtreated slowly with stirring with 5 mmol of Calcium Chloride as a 10%aqueous solution. The resulting slurry is filtered, washed and dried.The calcium soap is made in this way for each one of the preceding fattyacids listed above.

EXAMPLE 82 Magnesium Soaps

Sodium Soap made as per Example 78 (10 mmol) is dissolved in water andtreated slowly with stirring with 5 mmol of Magnesium Chloride as a 10%aqueous solution.

The resulting slurry is filtered, washed and dried. The magnesium soapis made in this way for each one of the preceding fatty acids listedabove.

INDUSTRIAL APPLICABILITY

The compositions, e.g., the various novel fatty acids and salts of thetype herein can be used in all manner of compositions. Detergentcompositions of the invention may also contain additional detergentcomponents. The precise nature of these additional components, andlevels of incorporation thereof will depend on the physical form of thecleaning composition, and the precise nature of the cleaning operationfor which it is to be used. Cleaning compositions herein include, butare not limited to: granular, bar-form and liquid laundry detergents;liquid hand dishwashing compositions; liquid, gel and bar-form personalcleansing products; shampoos; dentifrices; hard surface cleaners, andthe like. Such compositions can contain a variety of conventionaldetersive ingredients.

The compositions, e.g., the various novel fatty acids and salts of thetype herein can be used in all manner of skin care compositions. Theprecise nature of these additional components, and levels ofincorporation thereof will depend on the physical form of the skin carecomposition, and the precise nature of the skin care operation for whichit is to be used.

The following listing of such ingredients is for the convenience of theformulator, and not by way of limitation of the types of ingredientswhich can be used with the branched-chain surfactants herein. Thecleaning compositions of the invention preferably contain one or moreconventional detergent additives for example surfactants, builders,alkalinity system, organic polymeric compounds, suds suppressors, soilsuspension and anti-redeposition agents and corrosion inhibitors. Theskin care compositions of the invention preferably contain one or moreconventional skin care additives, for example, fragrances, emollients,anti-acne actives, thickeners, structuring agents and skin conditioners.

Conventional Detergent Additives

Detersive Surfactants:

The detergent compositions according to the present invention preferablyfurther comprise additional surfactants, herein also referred to asco-surfactants. It is to be understood that the branched-chainsurfactants prepared in the manner of the present invention may be usedsingly in cleaning compositions or in combination with other detersivesurfactants. Typically, fully-formulated cleaning compositions willcontain a mixture of surfactant types in order to obtain broad-scalecleaning performance over a variety of soils and stains and under avariety of usage conditions. One advantage of the branched-chainsurfactants herein is their ability to be readily formulated incombination with other known surfactant types.

A wide range of these co-surfactants can be used in the detergentcompositions of the present invention. A typical listing of anionic,nonionic, cationic, ampholytic and zwitterionic classes, and species ofthese co-surfactants, is given in U.S. Pat. No. 3,664,961 issued toNorris on May 23, 1972. Amphoteric surfactants are also described indetail in “Amphoteric Surfactants, Second Edition”, E. G. Lomax, Editor(published 1996, by Marcel Dekker, Inc.) McCutcheon's, Emulsifiers andDetergents, Annually published by M. C. Publishing Co., and SurfaceActive Agents and Detergents” (Vol. I and II by Schwartz, Perry andBerch) which are incorporated herein by reference.

The laundry detergent compositions of the present invention typicallycomprise from about 0.1% to about 50%, preferably from about 0.5% toabout 35%, more preferably 0.5% to about 30%, by weight ofco-surfactants. Selected co-surfactants are further identified asfollows.

Anionic Co-surfactants—Nonlimiting examples of anionic co-surfactantsuseful herein, typically at levels from about 0.1% to about 50%, byweight, include the conventional C₁₁-C₁₈ alkyl benzene sulfonates(“LAS”) and primary, branched-chain and random C₁₀-C₂₀ alkyl sulfates(“AS”), the C₁₀-C₁₈ secondary (2,3) alkyl sulfates of the formulaCH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺)CH₃ and CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺)CH₂CH₃ where xand (y+1) are integers of at least about 7, preferably at least about 9,and M is a water-solubilizing cation, especially sodium, unsaturatedsulfates such as oleyl sulfate, the C₁₀-C₁₈ alpha-sulfonated fatty acidesters, the C₁₀-C₁₈ sulfated alkyl polyglycosides, the C₁₀-C₁₈ alkylalkoxy sulfates (“AE_(x)S”; especially EO 1-7 ethoxy sulfates), andC₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates). The C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the overall compositions. C₁₀-C₂₀ conventional soaps may also beused. Other conventional useful anionic co-surfactants are listed instandard texts.

The alkyl alkoxy sulfate surfactants useful herein are preferably watersoluble salts or acids of the formula RO(A)_(m)SO₃M wherein R is anunsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkylcomponent, preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, more preferablyC₁₂-C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m isgreater than zero, typically between about 0.5 and about 6, morepreferably between about 0.5 and about 3, and M is H or a cation whichcan be, for example, a metal cation, ammnonium or substituted-ammoniumcation. Alkyl ethoxylated sulfates as well as alkyl propoxylatedsulfates are contemplated herein.

The alkyl sulfate surfactants useful herein are preferably water solublesalts or acids of the formula ROSO₃M wherein R preferably is a C₁₀-C₂₄hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₁₈ alkylcomponent, more preferably a C₁₂-C₁₅ alkyl or hydroxyalkyl, and M is Hor a cation, e.g., an alkali metal cation (e.g. sodium, potassium,lithium), or ammonium or substituted ammonium.

Other suitable anionic surfactants that can be used are alkyl estersulfonate surfactants including linear esters of C₈-C₂₀ carboxylic acids(i.e., fatty acids) which are sulfonated with gaseous SO₃ according to“The Journal of the American Oil Chemists Society”, 52 (1975), pp.323-329. Suitable starting materials would include natural fattysubstances as derived from tallow, palm oil, etc.

Other anionic co-surfactants useful for detersive purposes can also beincluded in the laundry detergent compositions of the present invention.These can include salts of soap, C₈-C₂₂ primary of secondaryalkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylicacids prepared by sulfonation of the pyrolyzed product of alkaline earthmetal citrates, e.g., as described in British patent specification No.1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerolsulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxideether sulfates, paraffin sulfonates, alkyl phosphates, isethionates suchas the acyl isethionates, N-acyl taurates, alkyl succinamates andsulfosuccinates, monoesters of sulfosuccinates (especially saturated andunsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates(especially saturated and unsaturated C₆-C₁₂ diesters), sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (thenonionic nonsulfated compounds being described below), and alkylpolyethoxy carboxylates such as those of the formulaRO(CH₂CH₂O)_(k)—CH₂COO—M+ wherein R is a C₈-C₂₂ alkyl, k is an integerfrom 0 to 10, and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenatedrosin, and resin acids and hydrogenated resin acids present in orderived from tall oil. A variety of such surfactants are also generallydisclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975 to Laughlin,et al. at Column 23, line 58 through Column 29, line 23 (hereinincorporated by reference).

Another possible surfactant are the so-called Dianionics. These aresurfactants which have at least two anionic groups present on thesurfactant molecule. Some suitable dianionic surfactants are furtherdescribed in WO 98/00498, WO 98/00503, U.S. Pat. No. 5,958,858, WO98/05742, WO 98/05749, the disclosures of which are incorporated hereinby reference. Other conventional useful surfactants are listed instandard texts.

Additionally, the surfactant may be a branched alkyl sulfate, branchcdalkyl alkoxylate, branched alkyl alkoxylate sulfate or mid chainbranched alkyl aryl sulfonate. These Surfactants are further describedin WO 99105243, WO 99/05242, WO 99105244, WO 99/05082, WO 99/05084.

WO 99/05241, WO 99/19434, WO 99/18929, WO 99/18929, WO 99/19448, WO9/19449. Other suitable midchain branched surfactants can be found in WO97/39087, WO 97/39088, WO 97/39091, WO 98/23712, WO 97/38972, WO97/39-89, WO 97/3900. Mixtures of these branched surfactants withconventional linear surfactants are also suitable for use in the presentcompositions.

Nonionic Co-surfactants—Nonlimiting examples of nonionic co-surfactantsuseful herein typically at levels from about 0.1% to about 50%, byweight include the alkoxylated alcohols (AE's) and alkyl phenols,polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's),C₁₀-C₁₈ glycerol ethers, and the like.

More specifically, the condensation products of primary and secondaryaliphatic alcohols with from about 1 to about 25 moles of ethylene oxide(AE) are suitable for use as the nonionic surfactant in the presentinvention. The alkyl chain of the aliphatic alcohol can either bestraight or branched, primary or secondary, and generally contains fromabout 8 to about 22 carbon atoms. Preferred are the condensationproducts of alcohols having an alkyl group containing from about 8 toabout 20 carbon atoms, with from about 1 to about 10 moles of ethyleneoxide per mole of alcohol. Especially preferred nonionic surfactants ofthis type are the C₉-C₁₅ primary alcohol ethoxylates containing 3-12moles of ethylene oxide per mole of alcohol, particularly the C₁₂-C₁₅primary alcohols containing 5-10 moles of ethylene oxide per mole ofalcohol.

Examples of commercially available nonionic surfactants of this typeinclude: Tergitol™ 15-S-9 (the condensation product of C₁₁-C₁₅ linearalcohol with 9 moles ethylene oxide) and Tergitol™ 24-L-6 NMW (thecondensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol™ 45-9 (the condensation product ofC₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3(the condensation product of C₁₂-C₁₃ linear alcohol with 3 moles ofethylene oxide), Neodol™ 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide) and Neodol™ 45-5 (thecondensation product of C₁₄-C₁₅ linear alcohol with 5 moles of ethyleneoxide) marketed by Shell Chemical Company; Kyro™ EOB (the condensationproduct of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide), marketed by TheProcter & Gamble Company; and Genapol LA O3O or O5O (the condensationproduct of C₁₂-C₁₄ alcohol with 3 or 5 moles of ethylene oxide) marketedby Hoechst. The preferred range of HLB in these AE nonionic surfactantsis from 8-17 and most preferred from 8-14. Condensates with propyleneoxide and butylene oxides may also be used.

Another class of preferred nonionic co-surfactants for use herein arethe polyhydroxy fatty acid amide surfactants of the formula.

wherein R¹ is H, or C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propylor a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₅₋₁₇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction. Typical examplesinclude the C₁₂-C₁₈ and C₁₂-C₁₄ N-methylglucamides. See U.S. Pat. Nos.5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can alsobe used; see U.S. Pat. No. 5,489,393.

Also useful as a nonionic co-surfactant in the present invention are thealkylpolysaccharides such as those disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, and EP-Patents B 0 070 077, 0 075 996 and0 094 118.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are also suitable for use as the nonionic surfactant of thesurfactant systems of the present invention, with the polyethylene oxidecondensates being preferred. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to about 14 carbon atoms, preferably from about 8 to about 14 carbonatoms, in either a straight-chain or branched-chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 2 to about 25 moles of ethyleneoxide per mole of alkyl phenol. Commercially available nonionicsurfactants of this type include Igepal™ CO-630, marketed by the GAFCorporation; and Triton™ X-45, X-114, X-100 and X-102, all marketed bythe Rohm & Haas Company. These surfactants are commonly referred to asalkylphenol alkoxylates (e.g., alkyl phenol ethoxylates). Examples ofother suitable nonionic surfactants are the commercially-availablePluronic™ surfactants, marketed by BASF, the commercially availableTetronic™ compounds, marketed by BASF.

Also preferred nonionics are amine oxide surfactants. The compositionsof the present invention may comprise amine oxide in accordance with thegeneral formula I:

R¹(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R′)₂.qH₂O  (I).

In general, it can be seen that the structure (I) provides onelong-chain moiety R¹(EO)_(x)(PO)_(y)(BO)_(z) and two short chainmoieties, CH₂R′. R′ is preferably selected from hydrogen, methyl and—CH₂OH. In general R¹ is a primary or branched hydrocarbyl moiety whichcan be saturated or unsaturated, preferably, R¹ is a primary alkylmoiety. When x+y+z=0, R¹ is a hydrocarbyl moiety having chainlength offrom about 8 to about 18. When x+y+z is different from 0, R¹ may besomewhat longer, having a chainlength in the range C₁₂-C₂₄. The generalformula also encompasses amine oxides wherein x+y+z=0, R¹=C₈-C₁₈, R′=Hand q=0-2, preferably 2. These amide oxides are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamineoxide and their hydrates, especially the dihydrates as disclosed in U.S.Pat. Nos. 5,075,501 and 5,071,594, incorporated herein by reference.

Highly preferred amine oxides herein are solutions at ambienttemperature. Amine oxides suitable for use herein are made commerciallyby a number of suppliers, including Akzo Chemie, Ethyl Corp., andProcter & Gamble. See McCutcheon's compilation and Kirk-Othmer reviewarticle for alternate amine oxide manufacturers.

Whereas in certain of the preferred embodiments R′ is H, there is somelatitude with respect to having R′ slightly larger than H. Specifically,the invention further encompasses embodiments wherein R′ is CH₂OH, suchas hexadecylbis(2-hydroxyethyl)amine oxide,tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amineoxide and oleylbis(2-hydroxyethyl)amine oxide, dodecyldimethylamineoxide dihydrate.

Cationic Co-surfactants—Nonlimiting examples of cationic co-surfactantsuseful herein typically at levels from about 0.1% to about 50%, byweight include the choline ester-type quats and alkoxylated quaternaryammonium (AQA) surfactant compounds, and the like.

Cationic co-surfactants useful as a component of the surfactant systemis a cationic choline ester-type quat surfactant which are preferablywater dispersible compounds having surfactant properties and comprise atleast one ester (i.e. —COO—) linkage and at least one cationicallycharged group. Suitable cationic ester surfactants, including cholineester surfactants, have for example been disclosed in U.S. Pat. Nos.4,228,042, 4,239,660 and 4,260,529.

Preferred cationic ester surfactants are those having the formula:

wherein R₁ is a C₅-C₃₁ linear or branched alkyl, alkenyl or alkarylchain or M⁻.N⁺(R₆R₇R₈)(CH₂)_(s); X and Y, independently, are selectedfrom the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONHand NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH orNHCOO group; R₂, R₃, R₄, R₆, R₇ and R₈ are independently selected fromthe group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl andalkaryl groups having from 1 to 4 carbon atoms; and R₅ is independentlyH or a C₁-C₃ alkyl group; wherein the values of m, n, s and tindependently lie in the range of from 0 to 8, the value of b lies inthe range from 0 to 20, and the values of a, u and v independently areeither 0 or 1 with the proviso that at least one of u or v must be 1;and wherein M is a counter anion.

Preferably R₂, R₃ and R₄ are independently selected from CH₃ and—CH₂CH₂OH.

Preferably M is selected from the group consisting of halide, methylsulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride,bromide or iodide.

Preferred water dispersible cationic ester surfactants are the cholineesters having the formula:

wherein R₁ is a C₁₁-C₁₉ linear or branched alkyl chain.

Other suitable cationic ester surfactants have the structural formulasbelow, wherein d may be from 0 to 20.

In a preferred aspect these cationic ester surfactant are hydrolysableunder the conditions of a laundry wash method.

Cationic co-surfactants useful herein also include alkoxylatedquaternary ammonium (AQA) surfactant compounds (referred to hereinafteras “AQA compounds”) having the formula:

wherein R¹ is a linear or branched alkyl or alkenyl moiety containingfrom about 8 to about 18 carbon atoms, preferably 10 to about 16 carbonatoms, most preferably from about 10 to about 14 carbon atoms; R² is analkyl group containing from one to three carbon atoms, preferablymethyl; R³ and R⁴ can vary independently and are selected from hydrogen(preferred), methyl and ethyl; X⁻ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, sufficient to provide electricalneutrality. A and A′ can vary independently and are each selected fromC₁-C₄ alkoxy, especially ethoxy (i.e., —CH₂CH₂O—), propoxy, butoxy andmixed ethoxy/propoxy; p is from 0 to about 30, preferably 1 to about 4and q is from 0 to about 30, preferably 1 to about 4, and mostpreferably to about 4; preferably both p and q are 1. See also: EP2,084, published May 30, 1979, by The Procter & Gamble Company, whichdescribes cationic co-surfactants of this type which are also usefulherein.

AQA compounds wherein the hydrocarbyl substituent R¹ is C₈-C₁₁,especially C₁₀, enhance the rate of dissolution of laundry granules,especially under cold water conditions, as compared with the higherchain length materials. Accordingly, the C₈-C₁₁ AQA surfactants may bepreferred by some formulators. The levels of the AQA surfactants used toprepare finished laundry detergent compositions can range from about0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.

Designation R¹ R² ApR³ A′gR⁴ AQA-1 C₁₂-C₁₄ CH₃ EO EO (also referred toas Coco Methyl EO2) AQA-2 C₁₂-C₁₆ CH₃ (EO)₂ EO AQA-3 C₁₂-C₁₄ CH₃ (EO)₂(EO)₂ (Coco Methyl EO4) AQA-4 C₁₂ CH₃ EO EO AQA-5 C₁₂-C₁₄ CH₃ (EO)₂(EO)₃ AQA-6 C₁₂-C₁₄ CH₃ (EO)₂ (EO)₃ AQA-7 C₈-C₁₈ CH₃ (EO)₃ (EO)₂ AQA-8C₁₂-C₁₄ CH₃ (EO)₄ (EO)₄ AQA-9 C₁₂-C₁₄ C₂H₅ (EO)₃ (EO)₃ AQA-10 C₁₂-C₁₈C₃H₇ (EO)₃ (EO)₄ AQA-11 C₁₂-C₁₈ CH₃ (propoxy) (EO)₃ AQA-12 C₁₀-C₁₈ C₂H₅(iso-propoxy)₂ (EO)₃ AQA-13 C₁₀-C₁₈ CH₃ (EO/PO)₂ (EO)₃ AQA-14 C₈-C₁₈ CH₃(EO)₁₅* (EO)₁₅* AQA-15 C₁₀ CH₃ EO EO AQA-16 C₈-C₁₂ CH₃ EO EO AQA-17C₉-C₁₁ CH₃ EO 3.5 Avg. AQA-18 C₁₂ CH₃ EO 3.5 Avg. AQA-19 C₈-C₁₄ CH₃(EO)₁₀ (EO)₁₀ AQA-20 C₁₀ C₂H₅ (EO)₂ (EO)₃ AQA-21 C₁₂-C₁₄ C₂H₅ (EO)₅(EO)₃ AQA-22 C₁₂-C₁₈ C₃H₇ Bu (EO)₂ *Ethoxy, optionally end-capped withmethyl or ethyl.

The preferred bis-ethoxylated cationic surfactants herein are availableunder the trade name ETHOQUAD from Akzo Nobel Chemicals Company.

Highly preferred bis-AQA compounds for use herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, preferably C₁₀,C₁₂, C₁₄ alkyl and mixtures thereof, and X is any convenient anion toprovide charge balance, preferably chloride. With reference to thegeneral AQA structure noted above, since in a preferred compound R¹ isderived from coconut (C₁₂-C₁₄ alkyl) fraction fatty acids, R² is methyland ApR³ and A′qR⁴ are each monoethoxy, this preferred type of compoundis referred to herein as “CocoMeEO2” or “AQA-1” in the above list.

Other preferred AQA compounds herein include compounds of the formula:

wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃alkyl, preferably methyl, and X is an anion, especially chloride.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂CH₂O) units (EO) are replaced by butoxy (Bu), isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

The following illustrates various other adjunct ingredients which may beused in the compositions of this invention, but is not intended to belimiting thereof. While the combination of the mid-chain branchedprimary alkyl surfactants with such adjunct compositional ingredientscan be provided as finished products in the form of liquids, gels, bars,or the like using conventional techniques, the manufacture of thegranular laundry detergents herein requires some special processingtechniques in order to achieve optimal performance. Accordingly, themanufacture of laundry granules will be described hereinafter separatelyin the Granules Manufacture section (below), for the convenience of theformulator.

Additional cationic co-surfactants are described, for example, in the“Surfactant Science Series, Volume 4, Cationic Surfactants” or in the“Industrial Surfactants Handbook”. Classes of useful cationicsurfactants described in these references include amide quats (i.e.,Lexquat AMG & Schercoquat CAS), glycidyl ether quats (i.e., Cyostat609), hydroxyalkyl quats (i.e., Dehyquart E), alkoxypropyl quats (i.e.,Tomah Q-17-2), polypropoxy quats (Emcol CC-9), cyclic alkylammoniumcompounds (i.e., pyridinium or imidazolinium quats), and/or benzalkoniumquats.

Detersive Enzymes—Enzymes are preferably included in the presentdetergent compositions for a variety of purposes, including removal ofprotein-based, carbohydrate-based, or triglyceride-based stains fromsubstrates, for the prevention of refugee dye transfer in fabriclaundering, and for fabric restoration. Recent enzyme disclosures indetergents useful herein include bleach/amylase/protease combinations(EP 755,999 A; EP 756,001 A; EP 756,000 A); chondriotinase (EP 747,469A); protease variants (WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO96/25489 A); xylanase (EP 709,452 A); keratinase (EP 747,470 A); lipase(GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154A); cellulase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A);thernitase (WO 96/28558 A). More generally, suitable enzymes includeproteases, amylases, lipases, cellulases, peroxidases, xylanases,keratinases, chondriotinases; thermitases, cutinases and mixturesthereof of any suitable origin, such as vegetable, animal, bacterial,fungal and yeast origin. Preferred selections are influenced by factorssuch as pH-activity and/or stability optima, thermostability, andstability to active detergents, builders and the like. In this respectbacterial or fungal enzymes are preferred, such as bacterial amylasesand proteases, and fungal cellulases. Suitable enzymes are alsodescribed in U.S. Pat. Nos. 5,677,272, 5,679,630, 5,703,027, 5,703,034,5,705,464, 5,707,950, 5,707,951, 5,710,115, 5,710,116, 5,710,118,5,710,119 and 5,721,202.

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry, hard surfacecleaning or personal care detergent composition. Preferred detersiveenzymes are hydrolases such as proteases, amylases and lipases.Preferred enzymes for laundry purposes include, but are not limited to,proteases, cellulases, lipases and peroxidases. Highly preferred areamylases and/or proteases, including both current commercially availabletypes and improved types which, though more and more bleach compatiblethough successive improvements, have a remaining degree of bleachdeactivation susceptibility.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a “cleaning-effectiveamount”. The term “cleaning effective amount” refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics, dishware and the like. In practical terms for currentcommercial preparations, typical amounts are up to about 5 mg by weight,more typically 0.01 mg to 3 mg, of active enzyme per gram of thedetergent composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. Protease enzymes are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition. For certaindetergents it may be desirable to increase the active enzyme content ofthe commercial preparation in order to minimize the total amount ofnon-catalytically active materials and thereby improve spotting/filmingor other end-results. Higher active levels may also be desirable inhighly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble. When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as“Protease D” is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76, preferably also in combination with one or more aminoacid residue positions equivalent to those selected from the groupconsisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,+128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,+222, +260, +265, and/or +274 according to the numbering of Bacillusamyloliquefaciens subtilisin, as described in WO 95/10615 published Apr.20, 1995 by Genencor International.

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Amylases suitable herein include, for example, α-amylases described inGB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. andTERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineeringof enzymes for improved stability, e.g., oxidative stability, is known.See, for example J. Biological Chem., Vol. 260, No. 11, Jun. 1985, pp.6518-6521. Certain preferred embodiments of the present compositions canmake use of amylases having improved stability in detergents, especiallyimproved oxidative stability as measured against a reference-point ofTERMAMYL® in commercial use in 1993. These preferred amylases hereinshare the characteristic of being “stability-enhanced” amylases,characterized, at a minimum, by a measurable improvement in one or moreof: oxidative stability, e.g., to hydrogenperoxide/tetraacetylethylenediamine in buffered solution at pH 9-10;thermal stability, e.g., at common wash temperatures such as about 60°C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597. Stability-enhanced amylasescan be obtained from Novo or from Genencor International. One class ofhighly preferred amylases herein have the commonality of being derivedusing site-directed mutagenesis from one or more of the Bacillusamylases, especially the Bacillus α-amylases, regardless of whether one,two or multiple amylase strains are the immediate precursors. Oxidativestability-enhanced amylases vs. the above-identified reference amylaseare preferred for use, especially in bleaching, more preferably oxygenbleaching, as distinct from chlorine bleaching, detergent compositionsherein. Such preferred amylases include (a) an amylase according to thehereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as furtherillustrated by a mutant in which substitution is made, using alanine orthreonine, preferably threonine, of the methionine residue located inposition 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®,or the homologous position variation of a similar parent amylase, suchas B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th Amnerican Chemical Society National Meeting, Mar. 13-17 1994, byC. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE® and SUNLIGHT®; (c) particularly preferred amylases hereininclude amylase variants having additional modification in the immediateparent as described in WO 9510603 A and are available from the assignee,Novo, as DURAMYL®. Other particularly preferred oxidative stabilityenhanced amylase include those described in WO 9418314 to GenencorInternational and WO 9402597 to Novo. Any other oxidativestability-enhanced amylase can be used, for example as derived bysite-directed mutagenesis from known chimeric, hybrid or simple mutantparent forms of available amylases. Other preferred enzyme modificationsare accessible. See WO 9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and in WO96/23873 Specific amylase enzymes for use in the detergent compositionsof the present invention include α-amylases characterized by having aspecific activity at least 25% higher than the specific activity ofTermamyl® at a temperature range of 25° C. to 55° C. and at a pH valuein the range of 8 to 10, measured by the Phadebas® α-amylase activityassay. (Such Phadebas® α-amylase activity assay is described at pages9-10, WO 95/26397.) Also included herein are α-amylases which are atleast 80% homologous with the amino acid sequences shown in the SEQ IDlistings in the references. These enzymes are preferably incorporatedinto laundry detergent compositions at a level from 0.00018% to 0.060%pure enzyme by weight of the total composition, more preferably from0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases usable herein include both bacterial and fungal types,preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307, Barbesgoard et al, Mar. 6, 1984, discloses suitable fungalcellulases from Humicola insolens or Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk,Dolabella Auricula Solander. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® andCELLUZYME®(Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open Feb. 24, 1978. This lipase isavailable from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under thetrade name Lipase P “Amano,” or “Amano-P.” Other suitable commerciallipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,Tagata, Japan; Chromobacter viscosum lipases from U.S. BiochemicalCorp., U.S.A. and Disoynth Co., The Netherlands, and lipases exPseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosaand commercially available from Novo, see also EP 341,947, is apreferred lipase for use herein. Lipase and amylase variants stabilizedagainst peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

Cutinase enzymes suitable for use herein are described in WO 8809367 Ato Genencor.

Peroxidase enzymes may be used in combination with oxygen sources, e.g.,percarbonate, perborate, hydrogen peroxide, etc., for “solutionbleaching” or prevention of transfer of dyes or pigments removed fromsubstrates during the wash to other substrates present in the washsolution. Known peroxidases include horseradish peroxidase, ligninase,and haloperoxidases such as chloro- or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr.14, 1981. Enzymes for use in detergents can be stabilized by varioustechniques. Enzyme stabilization techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilizationsystems are also described, for example, in U.S. Pat. No. 3,519,570. Auseful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, isdescribed in WO 9401532 A to Novo.

Builders—Detergent builders are preferably included in the compositionsherein, for example to assist in controlling mineral, especially Caand/or Mg, hardness in wash water or to assist in the removal and/orsuspension of particulate soils from surfaces and sometimes to providealkalinity and/or buffering action. In solid formulations, builderssometimes serve as absorbents for surfactants. Alternately, certaincompositions can be formulated with completely water-soluble builders,whether organic or inorganic, depending on the intended use.

Suitable silicate builders include water-soluble and hydrous solid typesand including those having chain-, layer-, orthree-dimensional-structure as well as amorphous-solid silicates orother types, for example especially adapted for use innon-structured-liquid detergents. Preferred are alkali metal silicates,particularly those liquids and solids having a SiO₂:Na₂O ratio in therange 1.6:1 to 3.2:1, including solid hydrous 2-ratio silicates marketedby PQ Corp. under the tradename BR TESIL®, e.g., BRITESIL H2O; andlayered silicates, e.g., those described in U.S. Pat. No. 4,664,839, May12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated “SKS-6”, is acrystalline layered aluminum-free δ-Na₂SiO₅ morphology silicate marketedby Hoechst and is preferred especially in granular laundry compositions.See preparative methods in German DE-A-3,417,649 and DE-A-3,742,043.Other layered silicates, such as those having the general formulaNaMSi_(x)O_(2x+1).yH₂O wherein M is sodium or hydrogen, x is a numberfrom 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably0, can also or alternately be used herein. Layered silicates fromHoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β and γlayer-silicate forms. Other silicates may also be useful, such asmagnesium silicate, which can serve as a crisping agent in granules, asa stabilizing agent for bleaches, and as a component of suds controlsystems.

Also suitable for use herein are synthesized crystalline ion exchangematerials or hydrates thereof having chain structure and a compositionrepresented by the following general formula in an anhydride form:xM₂O.ySiO₂.zM′O wherein M is Na and/or K, M′ is Ca and/or Mg; y/x is 0.5to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. Pat. No. 5,427,711,Sakaguchi et al, Jun. 27, 1995.

Aluminosilicate builders, such as zeolites, are especially useful ingranular detergents, but can also be incorporated in liquids, pastes orgels. Suitable for the present purposes are those having empiricalformula: [M_(z)(AlO₂)_(z)(SiO₂)_(v)].xH₂O wherein z and v are integersof at least 6, the molar ratio of z to v is in the range from 1.0 to0.5, and x is an integer from 15 to 264. Aluminosilicates can becrystalline or amorphous, naturally-occurring or synthetically derived.An aluminosilicate production method is in U.S. Pat. No. 3,985,669,Krummel, et al, Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials are available as Zeolite A,Zeolite P (B), Zeolite X and, to whatever extent this differs fromZeolite P, the so-called Zeolite MAP. Natural types, includingclinoptilolite, may be used. Zeolite A has the formula:Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O wherein x is from 20 to 30, especially 27.Dehydrated zeolites (x=0-10) may also be used. Preferably, thealuminosilicate has a particle size of 0.1-10 microns in diameter.

Builder level can vary widely depending upon end use and physical formof the composition. Built detergents typically comprise at least about1% builder. Liquid formulations typically comprise about 5% to about50%, more typically 5% to 35% of builder. Granular formulationstypically comprise from about 10% to about 80%, more typically 15% to50% builder by weight of the detergent composition. Lower or higherlevels of builders are not excluded. For example, certain detergentadditive or high-surfactant formulations can be unbuilt.

Suitable builders herein can be selected from the group consisting ofphosphates and polyphosphates, especially the sodium salts; carbonates,bicarbonates, sesquicarbonates and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, tri-, andtetracarboxylates especially water-soluble nonsurfactant carboxylates inacid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer carboxylatesincluding aliphatic and aromatic types; and phytic acid. These may becomplemented by borates, e.g., for pH-buffering purposes, or bysulfates, especially sodium sulfate and any other fillers or carrierswhich may be important to the engineering of stable surfactant and/orbuilder-containing detergent compositions.

Builder mixtures, sometimes termed “builder systems” can be used andtypically comprise two or more conventional builders, optionallycomplemented by chelants, pH-buffers or fillers, though these lattermaterials are generally accounted for separately when describingquantities of materials herein. In terms of relative quantities ofsurfactant and builder in the present detergents, preferred buildersystems are typically formulated at a weight ratio of surfactant tobuilder of from about 60:1 to about 1:80. Certain preferred laundrydetergents have said ratio in the range 0.90:1.0 to 4.0:1.0, morepreferably from 0.95:1.0 to 3.0:1.0.

P-containing detergent builders often preferred where permitted bylegislation include, but are not limited to, the alkali metal, ammoniumand alkanolanmmonium salts of polyphosphates exemplified by thetripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; andphosphonates.

Suitable carbonate builders include alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973, although sodium bicarbonate, sodiumcarbonate, sodium sesquicarbonate, and other carbonate minerals such astrona or any convenient multiple salts of sodium carbonate and calciumcarbonate such as those having the composition 2Na₂CO₃.CaCO₃ whenanhydrous, and even calcium carbonates including calcite, aragonite andvaterite, especially forms having high surface areas relative to compactcalcite may be useful, for example as seeds or for use in syntheticdetergent bars.

Suitable “organic detergent builders”, as described herein for use withthe alkylarylsulfonate surfactant system include polycarboxylatecompounds, including water-soluble nonsurfactant dicarboxylates andtricarboxylates. More typically builder polycarboxylates have aplurality of carboxylate groups, preferably at least 3 carboxylates.Carboxylate builders can be formulated in acid, partially neutral,neutral or overbased form. When in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.Polycarboxylate builders include the ether polycarboxylates, such asoxydisuccinate, see Berg, U.S. Pat. No. 3,128,287, Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, Jan. 18, 1972; “TMS/TDS”builders of U.S. Pat. No. 4,663,071, Bush et al, May 5, 1987; and otherether carboxylates including cyclic and alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

Other suitable organic detergent builders are the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether; 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid;carboxymethyloxysuccinic acid; the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as mellitic acid,succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof are importantcarboxylate builders e.g., for heavy duty liquid detergents, due toavailability from renewable resources and biodegradability. Citrates canalso be used in granular compositions, especially in combination withzeolite and/or layered silicates. Oxydisuccinates are also especiallyuseful in such compositions and combinations.

Where permitted, and especially in the formulation of bars used forhand-laundering operations, alkali metal phosphates such as sodiumtripolyphosphates, sodium pyrophosphate and sodium orthophosphate can beused. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonateand other known phosphonates, e.g., those of U.S. Pat. Nos. 3,159,581;3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and mayhave desirable antiscaling properties.

Certain detersive surfactants or their short-chain homologues also havea builder action. For unambiguous formula accounting purposes, when theyhave surfactant capability, these materials are summed up as detersivesurfactants. Preferred types for builder functionality are illustratedby: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986. Succinic acidbuilders include the C₅-C₂₀ alkyl and alkenyl succinic acids and saltsthereof. Succinate builders also include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Lauryl-succinates are describedin European Patent Application 86200690.5/0,200,263, published Nov. 5,1986. Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions as surfactant/builder materials aloneor in combination with the aforementioned builders, especially citrateand/or the succinate builders, to provide additional builder activity.Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, Mar. 7, 1967. See also Diehl, U.S. Pat. No. 3,723,322.

Other types of inorganic builder materials which can be used have theformula (M_(x))_(i)Ca_(y)(CO₃)_(z) wherein x and i are integers from 1to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_(i)are cations, at least one of which is a water-soluble, and the equationΣ_(i=1-15)(x_(i) multiplied by the valence of M_(i))+2y=2z is satisfiedsuch that the formula has a neutral or “balanced” charge. These buildersare referred to herein as “Mineral Builders”, examples of thesebuilders, their use and preparation can be found in U.S. Pat. No.5,707,959. Another suitable class of inorganic builders are theMagnesiosilicates, see WO97/0179.

Bleaching Agents—Preferred compositions of the present inventioncomprise, as part or all of the laundry or cleaning adjunct materials, ableaching agent. Oxygen bleaching agents useful in the present inventioncan be any of the oxidizing agents known for laundry, hard surfacecleaning, automatic dishwashing or denture cleaning purposes. Oxygenbleaches or mixtures thereof are preferred, though other oxidantbleaches, such as oxygen, an enzymatic hydrogen peroxide producingsystem, or hypohalites such as chlorine bleaches like hypochlorite, mayalso be used.

Common oxygen bleaches of the peroxygen type include hydrogen peroxide,inorganic peroxohydrates, organic peroxohydrates and the organicperoxyacids, including hydrophilic and hydrophobic mono- ordi-peroxyacids. These can be peroxycarboxylic acids, peroxyimidic acids,amidoperoxycarboxylic acids, or their salts including the calcium,magnesium, or mixed-cation salts. Peracids of various kinds can be usedboth in free form and as precursors known as “bleach activators” or“bleach promoters” which, when combined with a source of hydrogenperoxide, perhydrolyze to release the corresponding peracid.

Also useful herein as oxygen bleaches are the inorganic peroxides suchas Na₂O₂, superoxides such as KO₂, organic hydroperoxides such as cumenehydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacidsand their salts such as the peroxosulfuric acid salts, especially thepotassium salts of peroxodisulfuric acid and, more preferably, ofperoxomonosulfuric acid including the commercial triple-salt form soldas OXONE by DuPont and also any equivalent commercially available formssuch as CUROX from Akzo or CAROAT from Degussa. Certain organicperoxides, such as dibenzoyl peroxide, may be useful, especially asadditives rather than as primary oxygen bleach.

Mixed oxygen bleach systems are generally useful, as are mixtures of anyoxygen bleaches with the known bleach activators, organic catalysts,enzymatic catalysts and mixtures thereof; moreover such mixtures mayfurther include brighteners, photobleaches and dye transfer inhibitorsof types well-known in the art.

Preferred oxygen bleaches, as noted, include the peroxohydrates,sometimes known as peroxyhydrates or peroxohydrates. These are organicor, more comunonly, inorganic salts capable of releasing hydrogenperoxide readily. Peroxohydrates are the most common examples of“hydrogen peroxide source” materials and include the perborates,percarbonates, perphosphates, and persilicates. Suitable peroxohydratesinclude sodium carbonate peroxyhydrate and equivalent commercial“percarbonate” bleaches, and any of the so-called sodium perboratehydrates, the “tetrahydrate” and “monohydrate” being preferred; thoughsodium pyrophosphate peroxyhydrate can be used. Many such peroxohydratesare available in processed forms with coatings, such as of silicateand/or borate and/or waxy materials and/or surfactants, or have particlegeometries, such as compact spheres, which improve storage stability. Byway of organic peroxohydrates, urea peroxyhydrate can also be usefulherein.

Percarbonate bleach includes, for example, dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Percarbonates and perborates are widely available in commerce, forexample from FMC, Solvay and Tokai Denka.

Organic percarboxylic acids useful herein as the oxygen bleach includemagnesium monoperoxyphthalate hexahydrate, available from Interox,m-chloro perbenzoic acid and its salts, 4-nonylamino-4-oxoperoxybutyricacid and diperoxydodecanedioic acid and their salts. Such bleaches aredisclosed in U.S. Pat. No. 4,483,781, U.S. patent application Ser. No.740,446, Burns et al, filed Jun. 3, 1985, EP-A 133,354, published Feb.20, 1985, and U.S. Pat. No. 4,412,934. Organic percarboxylic acidsusable herein include those containing one, two or more peroxy groups,and can be aliphatic or aromatic. Highly preferred oxygen bleaches alsoinclude 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described inU.S. Pat. No. 4,634,551.

An extensive and exhaustive listing of useful oxygen bleaches, includinginorganic peroxohydrates, organic peroxohydrates and the organicperoxyacids, including hydrophilic and hydrophobic mono- ordi-peroxyacids, peroxycarboxylic acids, peroxyimidic acids,amidoperoxycarboxylic acids, or their salts including the calcium,magnesium, or mixed-cation salts, can be found in U.S. Pat. Nos.5,622,646 and 5,686,014.

Other useful peracids and bleach activators herein are in the family ofimidoperacids and imido bleach activators. These includephthaloylimidoperoxycaproic acid and related arylimido-substituted andacyloxynitrogen derivatives. For listings of such compounds,preparations and their incorporation into laundry compositions includingboth granules and liquids, See U.S. Pat. No. 5,487,818; U.S. Pat. No.5,470,988, U.S. Pat. No. 5,466,825; U.S. Pat. No. 5,419,846; U.S. Pat.No. 5,415,796; U.S. Pat. No. 5,391,324; U.S. Pat. No. 5,328,634; U.S.Pat. No. 5,310,934; U.S. Pat. No. 5,279,757; U.S. Pat. No. 5,246,620;U.S. Pat. No. 5,245,075; U.S. Pat. No. 5,294,362; U.S. Pat. No.5,423,998; U.S. Pat. No. 5,208,340; U.S. Pat. No. 5,132,431 and U.S.Pat. No. 5,087,385.

Useful diperoxyacids include, for example, 1,12-diperoxydodecanedioicacid (DPDA); 1,9-diperoxyazelaic acid; diperoxybrassilic acid;diperoxysebasic acid and diperoxyisophthalic acid;2-decyldiperoxybutane-1,4-dioic acid; and 4,4′-sulphonylbisperoxybenzoicacid.

More generally, the terms “hydrophilic” and “hydrophobic” used herein inconnection with any of the oxygen bleaches, especially the peracids, andin connection with bleach activators, are in the first instance based onwhether a given oxygen bleach effectively performs bleaching of fugitivedyes in solution thereby preventing fabric graying and discolorationand/or removes more hydrophilic stains such as tea, wine and grapejuice—in this case it is termed “hydrophilic”. When the oxygen bleach orbleach activator has a significant stain removal, whiteness-improving orcleaning effect on dingy, greasy, carotenoid, or other hydrophobicsoils, it is termed “hydrophobic”. The terms are applicable also whenreferring to peracids or bleach activators used in combination with ahydrogen peroxide source. The current commercial benchmarks forhydrophilic performance of oxygen bleach systems are: TAED or peraceticacid, for benchmarking hydrophilic bleaching. NOBS or NAPAA are thecorresponding benchmarks for hydrophobic bleaching. The terms“hydrophilic”, “hydrophobic” and “hydrotropic” with reference to oxygenbleaches including peracids and here extended to bleach activator havealso been used somewhat more narrowly in the literature. See especiallyKirk Othmer's Encyclopedia of Chemical Technology, Vol. 4., pages284-285. This reference provides a chromatographic retention time andcritical micelle concentration-based set of criteria, and is useful toidentify and/or characterize preferred sub-classes of hydrophobic,hydrophilic and hydrotropic oxygen bleaches and bleach activators thatcan be used in the present invention.

While not preferred for compositions of the present invention whichcomprise detersive enzymes, the present invention compositions may alsocomprise as the bleaching agent a chlorine-type bleaching material. Suchagents are well known in the art, and include for example sodiumdichloroisocyanurate (“NaDCC”), or sodium hypochlorite (NaOCl).

Bleach Activators

Bleach activators useful herein include anides, imides, esters andanhydrides. Commonly at least one substituted or unsubstituted acylmoiety is present, covalently connected to a leaving group as in thestructure R—C(O)—L. In one preferred mode of use, bleach activators arecombined with a source of hydrogen peroxide, such as the perborates orpercarbonates, in a single product. Conveniently, the single productleads to in situ production in aqueous solution (i.e., during thewashing process) of the percarboxylic acid corresponding to the bleachactivator. The product itself can be hydrous, for example a powder,provided that water is controlled in amount and mobility such thatstorage stability is acceptable. Alternately, the product can be ananhydrous solid or liquid. In another mode, the bleach activator oroxygen bleach is incorporated in a pretreatment product, such as a stainstick; soiled, pretreated substrates can then be exposed to furthertreatments, for example of a hydrogen peroxide source. With respect tothe above bleach activator structure RC(O)L, the atom in the leavinggroup connecting to the peracid-forming acyl moiety R(C)O— is mosttypically O or N. Bleach activators can have non-charged, positively ornegatively charged peracid-forming moieties and/or noncharged,positively or negatively charged leaving groups. One or moreperacid-forming moieties or leaving-groups can be present. See, forexample, U.S. Pat. No. 5,595,967, U.S. Pat. No. 5,561,235, U.S. Pat. No.5,560,862 or the bis-(peroxy-carbonic) system of U.S. Pat. No.5,534,179. Mixtures of suitable bleach activators can also be used.Bleach activators can be substituted with electron-donating orelectron-releasing moieties either in the leaving-group or in theperacid-forming moiety or moieties, changing their reactivity and makingthem more or less suited to particular pH or wash conditions. Forexample, electron-withdrawing groups such as NO₂ improve the efficacy ofbleach activators intended for use in mild-pH (e.g., from about 7.5- toabout 9.5) wash conditions.

An extensive and exhaustive disclosure of suitable bleach activators andsuitable leaving groups, as well as how to determine suitableactivators, can be found in U.S. Pat. Nos. 5,686,014 and 5,622,646.

Cationic bleach activators include quaternary carbamate-, quaternarycarbonate-, quaternary ester- and quaternary amide-types, delivering arange of cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acidsto the wash. An analogous but non-cationic palette of bleach activatorsis available when quaternary derivatives are not desired. In moredetail, cationic activators include quaternary amnmonium-substitutedactivators of WO 96-06915, U.S. Pat. No. 4,751,015 and 4,397,757,EP-A-284292, EP-A-331,229 and EP-A-03520. Also useful are cationicnitrites as disclosed in EP-A-303,520 and in European PatentSpecification 458,396 and 464,880. Other nitrite types haveelectron-withdrawing substituents as described in U.S. Pat. No.5,591,378.

Other bleach activator disclosures include GB 836,988; 864,798; 907,356;1,003,310 and 1,519,351; Germnan Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393, and the phenol sulfonate ester ofalkanoyl aminoacids disclosed in U.S. Pat. No. 5,523,434. Suitablebleach activators include any acetylated diamine types, whetherhydrophilic or hydrophobic in character.

Of the above classes of bleach precursors, preferred classes include theesters, including acyl phenol sulfonates, acyl alkyl phenol sulfonatesor acyl oxybenzenesulfonates (OBS leaving-group); the acyl-amides; andthe quaternary ammonium substituted peroxyacid precursors including thecationic nitriles.

Preferred bleach activators include N,N,N′N′-tetraacetyl ethylenediamine (TAED) or any of its close relatives including the triacetyl orother unsymmetrical derivatives. TAED and the acetylated carbohydratessuch as glucose pentaacetate and tetraacetyl xylose are preferredhydrophilic bleach activators. Depending on the application, acetyltriethyl citrate, a liquid, also has some utility, as does phenylbenzoate.

Preferred hydrophobic bleach activators include sodiumnonanoyloxybenzene sulfonate (NOBS or SNOBS),N-(alkanoyl)aminoalkanoyloxy benzene sulfonates, such as4-[N-(nonanoyl)aminohexanoyloxy]-benzene sulfonate or (NACA-OBS) asdescribed in U.S. Pat. No. 5,534,642 and in EPA 0 355 384 A1,substituted amide types described in detail hereinafter, such asactivators related to NAPAA, and activators related to certainimidoperacid bleaches, for example as described in U.S. Pat. No.5,061,807, issued Oct. 29, 1991 and assigned to HoechstAktiengesellschaft of Frankfurt, Germany and Japanese Laid-Open PatentApplication (Kokai) No. 4-28799.

Another group of peracids and bleach activators herein are thosederivable from acyclic imidoperoxycarboxylic acids and salts thereof,See U.S. Pat. No. 5,415,796, and cyclic imidoperoxycarboxylic acids andsalts thereof, see U.S. Pat. Nos. 5,061,807, 5,132,431, 5,6542,69,5,246,620, 5,419,864 and 5,438,147.

Other suitable bleach activators include sodium-4-benzoyloxy benzenesulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate;sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethyl anumoniumtoluyloxy-benzene sulfonate; or sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate (STHOBS).

Bleach activators may be used in an amount of up to 20%, preferably from0.1-10% by weight, of the composition, though higher levels, 40% ormore, are acceptable, for example in highly concentrated bleach additiveproduct forms or forms intended for appliance automiated dosing.

Highly preferred bleach activators useful herein are amide-substitutedand an extensive and exhaustive disclosure of these activators can befound in U.S. Pat. Nos. 5,686,014 and 5,622,646.

Other useful activators, disclosed in U.S. Pat. No. 4,966,723, arebenzoxazin-type, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—. A highly preferred activator ofthe benzoxazin-type is:

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having with in-use pH offrom about 6 to about 13, preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators are very useful herein, especially the acylcaprolactams (see for example WO 94-28102 A) and acyl valerolactams (seeU.S. Pat. No. 5,503,639). See also U.S. Pat. No. 4,545,784 whichdiscloses acyl caprolactams, including benzoyl caprolactam adsorbed intosodium perborate. In certain preferred embodiments of the invention,NOBS, lactam activators, imide activators or amide-functionalactivators, especially the more hydrophobic derivatives, are desirablycombined with hydrophilic activators such as TAED, typically at weightratios of hydrophobic activator: TAED in the range of 1:5 to 5:1,preferably about 1:1. Other suitable lactam activators arealpha-modified, see WO 96-22350 A1, Jul. 25, 1996. Lactam activators,especially the more hydrophobic types, are desirably used in combinationwith TAED, typically at weight ratios of amido-derived or caprolactamactivators:TAED in the range of 1:5 to 5:1, preferably about 1:1. Seealso the bleach activators having cyclic amidine leaving-group disclosedin U.S. Pat. No. 5,552,556.

Nonlimiting examples of additional activators useful herein are to befound in U.S. Pat. No. 4,915,854, U.S. Pat. Nos. 4,412,934 and4,634,551. The hydrophobic activator nonanoyloxybenzene sulfonate (NOBS)and the hydrophilic tetraacetyl ethylene diamine (TAED) activator aretypical, and mixtures thereof can also be used.

Additional activators useful herein include those of U.S. Pat. No.5,545,349.

Transition Metal Bleach Catalysts:

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. No. 5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416;U.S. Pat. No. 5,114.606; European Pat. App. Pub. Nos. 549,271A1,549,272A1, 544,440A2; 544,490A1; and WO 98/39405, WO 98/39335, WO98/39406. WO 98/39098; Preferred examples of these catalysts includeMn^(IV) ₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(PF₆)₂,Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimetiyl-1,4,7-triazacyclononane)—(OCH₃)₃(PF₆), andmixtures thereof, Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. Nos. 4,430,243, 5,114,611, 5,622,646 and5,686,014. The use of manganese with various complex ligands to enhancebleaching is also reported in the following U.S. Pat. Nos.: 4,728,455;5,284,944; 5,246,612, 5,256,779; 5,280,117; 5,274,147; 5,153,161; and5,227,084.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in M. L. Tobe, “Base Hydrolysis of Transition-Metal Complexes”,Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferredcobalt catalyst useful herein are cobalt pentaamine acetate salts havingthe formula [Co(NH₃)₅OAc]Ty, wherein “OAc” represents an acetate moietyand “Ty” is an anion, and especially cobalt pentaamine acetate chloride,[Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂;[Co(NH₃)₅OAc](SO₄); [Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂ (herein“PAC”). These cobalt catalysts are readily prepared by known procedures,such as taught for example in the Tobe article and the references citedtherein, and in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7,1989.

Compositions herein may also suitably include as a bleach catalyst theclass of transition metal complexes of a nacropolycyclic rigid ligand.The phrase “macropolycyclic rigid ligand” is sometimes abbreviated as“MRL”. One useful MRL is [MnByclamCl2], where “Bcyclam” is(5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane). See WO98/39405, WO 98/39335, WO 98/39406, WO 98/39098. The amount used is acatalytically effective amount, suitably about 1 ppb or more, forexample up to about 99.9%, more typically about 0.001 ppm or more,preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotesparts per billion by weight and “ppm” denotes parts per million byweight).

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the cleaningcompositions.

Enzymatic Sources of Hydrogen Peroxide

On a different track from the bleach activators illustrated hereinabove,another suitable hydrogen peroxide generating system is a combination ofa C₁-C₄ alkanol oxidase and a C₁-C₄ alkanol, especially a combination ofmethanol oxidase (MOX) and ethanol. Such combinations are disclosed inWO 94/03003. Other enzymatic materials related to bleaching, such asperoxidases, haloperoxidases, oxidases, superoxide dismutases, catalasesand their enhancers or, more commonly, inhibitors, may be used asoptional ingredients in the instant compositions.

Oxygen Transfer Agents and Precursors

Also useful herein are any of the known organic bleach catalysts, oxygentransfer agents or precursors therefor. These include the compoundsthemselves and/or their precursors, for example any suitable ketone forproduction of dioxiranes and/or any of the hetero-atom containinganalogs of dioxirane precursors or dioxiranes , such as sulfoniminesR¹R²C═NSO₂R³, see EP 446 982 A, published 1991 and sulfonyloxaziridines,see EP 446,981 A, published 1991. Preferred examples of such materialsinclude hydrophilic or hydrophobic ketones, used especially inconjunction with monoperoxysulfates to produce dioxiranes in situ,and/or the imines described in U.S. Pat. No. 5,576,282 and referencesdescribed therein. Oxygen bleaches preferably used in conjunction withsuch oxygen transfer agents or precursors include percarboxylic acidsand salts, percarbonic acids and salts, peroxymonosulfuric acid andsalts, and mixtures thereof. See also U.S. Pat. No. 5,360,568; U.S. Pat.No. 5,360,569; U.S. Pat. No. 5,370,826 and U.S. Pat. No. 5,442,066.

Although oxygen bleach systems and/or their precursors may besusceptible to decomposition during storage in the presence of moisture,air (oxygen and/or carbon dioxide) and trace metals (especially rust orsimple salts or colloidal oxides of the transition metals) and whensubjected to light, stability can be improved by adding commonsequestrants (chelants) and/or polymeric dispersants and/or a smallamount of antioxidant to the bleach system or product. See, for example,U.S. Pat. No. 5,545,349. Antioxidants are often added to detergentingredients ranging from enzymes to surfactants. Their presence is notnecessarily inconsistent with use of an oxidant bleach; for example, theintroduction of a phase barrier may be used to stabilize an apparentlyincompatible combination of an enzyme and antioxidant, on one hand, andan oxygen bleach, on the other. Although commonly known substances canbe used as antioxidants, For example see U.S. Pat. Nos. 5,686,014,5,622,646, 5,055,218, 4,853,143, 4,539,130 and 4,483,778. Preferredantioxidants are 3,5-di-tert-butyl-4-hydroxytoluene,2,5-di-tert-butylhydroquinone and D,L-alpha-tocopherol.

Polymeric Soil Release Agent—The compositions according to the presentinvention may optionally comprise one or more soil release agents.Polymeric soil release agents are characterized by having bothhydrophilic segments, to hydrophilize the surface of hydrophobic fibers,such as polyester and nylon, and hydrophobic segments, to deposit uponhydrophobic fibers and remain adhered thereto through completion of thelaundry cycle and, thus, serve as an anchor for the hydrophilicsegments. This can enable stains occurring subsequent to treatment withthe soil release agent to be more easily cleaned in later washingprocedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10% preferably from about 0.1% to about 5%, morepreferably from about 0.2% to about 3% by weight, of the composition.

The following, all included herein by reference, describe soil releasepolymers suitable for us in the present invention. U.S. Pat. No.5,691,298 Gosselink et al., issued Nov. 25, 1997; U.S. Pat. No.5,599,782 Pan et al., issued Feb. 4, 1997; U.S. Pat. No. 5,415,807Gosselink et al., issued May 16, 1995; U.S. Pat. No. 5,182,043 Morrallet al., issued Jan. 26, 1993; U.S. Pat. No. 4,956,447 Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 4,976,879 Maldonado et al. issuedDec. 11, 1990; U.S. Pat. No. 4,968,451 Scheibel et al., issued Nov. 6,1990; U.S. Pat. No. 4,925,577 Borcher, Sr. et al., issued May 15, 1990;U.S. Pat. No. 4,861,512 Gosselink, issued Aug. 29, 1989; U.S. Pat. No.4,877,896 Maldonado et al., issued Oct. 31, 1989; U.S. Pat. No.4,702,857 Gosselink et al., issued Oct. 27, 1987; U.S. Pat. No.4,711,730 Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580Gosselink issued Jan. 26, 1988; U.S. Pat. No. 4,000,093 Nicol et al.,issued Dec. 28, 1976; U.S. Pat. No. 3,959,230 Hayes, issued May 25,1976; U.S. Pat. No. 3,893,929 Basadur, issued Jul. 8, 1975; and EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. Pat. No.4,201,824 Voilland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681 Ruppert et al.;U.S. Pat. No. 4,220,918; U.S. Pat. No. 4,787,989; EP 279,134 A, 1988 toRhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 toUnilever N.V., 1974; all incorporated herein by reference.

Clay Soil Removal/Anti-redeposition Agents—The compositions of thepresent invention can also optionally contain water-soluble ethoxylatedamines having clay soil removal and antiredeposition properties.Granular detergent compositions which contain these compounds typicallycontain from about 0.01% to about 10.0% by weight of the water-solubleethoxylated amines; liquid detergent compositions typically containabout 0.01% to about 5%.

A preferred soil release and anti-redeposition agent is ethoxylatedtetraethylene pentamine. Exemplary ethoxylated amines are furtherdescribed in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1, 1986.Another group of preferred clay soil removal—antiredeposition agents arethe cationic compounds disclosed in European Patent Application 111,965,Oh and Gosselink, published Jun. 27, 1984. Other clay soilremoval/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/orantiredeposition agents known in the art can also be utilized in thecompositions herein. See U.S. Pat. No. 4,891,160, VanderMeer, issuedJan. 2, 1990 and WO 95/32272, published Nov. 30, 1995. Another type ofpreferred antiredeposition agent includes the carboxy methyl cellulose(CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents—Polymeric dispersing agents canadvantageously be utilized at levels from about 0.1% to about 7%, byweight, in the compositions herein, especially in the presence ofzeolite and/or layered silicate builders. Suitable polymeric dispersingagents include polymeric polycarboxylates and polyethylene glycols,although others known in the art can also be used. It is believed,though it is not intended to be limited by theory, that polymericdispersing agents enhance overall detergent builder performance, whenused in combination with other builders (including lower molecularweight polycarboxylates) by crystal growth inhibition, particulate soilrelease, peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. The average molecular weight of such polymers in the acidform preferably ranges from about 2,000 to 10,000, more preferably fromabout 4,000 to 7,000 and most preferably from about 4,000 to 5,000.Soluble polymers of this type are known materials. Use of polyacrylatesof this type in detergent compositions has been disclosed, for example,in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of, the dispersing/anti-redeposition agent. The averagemolecular weight of such copolymers in the acid form preferably rangesfrom about 2,000 to 100,000, more preferably from about 5,000 to 75,000,most preferably from about 7,000 to 65,000. The ratio of acrylate tomaleate segments in such copolymers will generally range from about 30:1to about 1:1, more preferably from about 10:1 to 2:1. Solubleacrylate/maleate copolymers of this type are known materials which aredescribed in European Patent Application No. 66915, published Dec. 15,1982, as well as in EP 193,360, published Sep. 3, 1986, which alsodescribes such polymers comprising hydroxypropylacrylate. Still otheruseful dispersing agents include the maleic/acrylic/vinyl alcoholterpolymers. Such materials are also disclosed in EP 193,360, including,for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal—antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Other polymer types which may be more desirable for biodegradability,improved bleach stability, or cleaning purposes include variousterpolymers and hydrophobically modified copolymers, including thosemarketed by Rohm & Haas, BASF Corp., Nippon Shokubai and others for allmanner of water-treatment, textile treatment, or detergent applications.

Brightener—Any optical brighteners or other brightening or whiteningagents known in the art can be incorporated at levels typically fromabout 0.01% to about 1.2%, by weight, into the detergent compositionsherein when they are designed for fabric washing or treatment.

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Arctic White CC and Arctic White CWD, the2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;4,4′-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4′-bis(styryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene;1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-styryl-naptho[1,2-d]oxazole; and2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton.

Polymeric Dye Transfer Inhibiting Agents—The compositions of the presentinvention may also include one or more materials effective forinhibiting the transfer of dyes from one fabric to another during thecleaning process. Generally, such dye transfer inhibiting agents includepolyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymersof N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

The amine N-oxide polymers typically have a ratio of amine to the amineN-oxide of 10:1 to 1:1,000,000. However, the number of amine oxidegroups present in the polyamine oxide polymer can be varied byappropriate copolymerization or by an appropriate degree of N-oxidation.The polyamine oxides can be obtained in almost any degree ofpolymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as “PVNO”. See U.S. Pat. No. 5,633,255 to Fredj.

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as “PVPVI”) are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol. 113.“Modem Methods of Polymer Characterization”, the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apolyvinylpyrrolidone (“PVP”) having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol (“PEG”)having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present inventioninclude, for example4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt (Tinopal-UNPA-GX),4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt (Tinopal 5BM-GX) and4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt (Tinopal AMS-GX) all by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the presentinvention provide especially effective dye transfer inhibitionperformance benefits when used in combination with the selectedpolymeric dye transfer inhibiting agents hereinbefore described. Thecombination of such selected polymeric materials (e.g., PVNO and/orPVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX,Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dyetransfer inhibition in aqueous wash solutions than does either of thesetwo detergent composition components when used alone. Without beingbound by theory the extent to which brighteners deposit on fabrics inthe wash solution can be defined by a parameter called the “exhaustioncoefficient”. The exhaustion coefficient is in general defined as theratio of a) the brightener material deposited on fabric to b) theinitial brightener concentration in the wash liquor. Brighteners withrelatively high exhaustion coefficients are the most suitable forinhibiting dye transfer in the context of the present invention.

Other, conventional optical brightener types can optionally be used inthe present compositions to provide conventional fabric “brightness”benefits, rather than a dye transfer inhibiting effect. Such usage isconventional and well-known to detergent formulations.

Chelating Agents—The detergent compositions herein may also optionallycontain one or chelating agents, particularly chelating agents foradventitious transition metals. Those commonly found in wash waterinclude iron and/or manganese in water-soluble, colloidal or particulateform, and may be associated as oxides or hydroxides, or found inassociation with soils such as humic substances. Preferred chelants arethose which effectively control such transition metals, especiallyincluding controlling deposition of such transition-metals or theircompounds on fabrics and/or controlling undesired redox reactions in thewash medium and/or at fabric or hard surface interfaces. Such chelatingagents include those having low molecular weights as well as polymerictypes, typically having at least one, preferably two or more donorheteroatoms such as O or N, capable of co-ordination to atransition-metal, Common chelating agents can be selected from the groupconsisting of aminocarboxylates, aminophosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof, all as hereinafter defined.

Aminocarboxylates useful as optional chelating agents includeethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetrapropionates,triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, andethanoldiglycines, their alkali metal, ammonium, and substitutedammonium salts, and mixtures thereof

Aminophosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) such as DEQUEST.Preferably, these amino phosphonates do not contain alkyl or alkenylgroups having more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, chelating agents will generally comprise from about 0.001%to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, chelating agents will comprise from about 0.01%to about 3.0% by weight of such compositions.

Suds Suppressors—Compounds for reducing or suppressing the formation ofsuds can be incorporated into the compositions of the present inventionwhen required by the intended use, especially washing of laundry inwashing appliances. Other compositions, such as those designed forhand-washing, may desirably be high-sudsing and may omit suchingredients Suds suppression can be of particular importance in theso-called “high concentration cleaning process” as described in U.S.Pat. No. 4,489,455 and 4,489,574 and in front-loading European-stylewashing machines.

A wide variety of materials may be used as suds suppressors and are wellknown in the art. See, for example, Kirk Othmer Encyclopedia of ChemicalTechnology, Third Edition, Volume 7, pages 430-447 (Wiley, 1979).

The compositions herein will generally comprise from 0% to about 10% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts thereof, will be present typically in amounts up toabout 5%, preferably 0.5%-3% by weight, of the detergent compositionalthough higher amounts may be used. Preferably from about 0.01% toabout 1% of silicone suds suppressor is used, more preferably from about0.25% to about 0.5%. These weight percentage values include any silicathat may be utilized in combination with polyorganosiloxane, as well asany suds suppressor adjunct materials that may be utilized. Monostearylphosphate suds suppressors are generally utilized in amounts rangingfrom about 0.1% to about 2%, by weight, of the composition. Hydrocarbonsuds suppressors are typically utilized in amounts ranging from about0.01% to about 5.0%, although higher levels can be used. The alcoholsuds suppressors are typically used at 0.2%-3% by weight of the finishedcompositions.

Alkoxylated Polycarboxylates—Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are useful herein to provide additionalgrease removal performance. Such materials are described in WO 91/08281and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.Chemically, these materials comprise polyacrylates having one ethoxyside-chain per every 7-8 acrylate units. The side-chains are of theformula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. Theside-chains are ester-linked to the polyacrylate “backbone” to provide a“comb” polymer type structure. The molecular weight can vary, but istypically in the range of about 2000 to about 50,000. Such alkoxylatedpolycarboxylates can comprise from about 0.05% to about 10%, by weight,of the compositions herein.

Fabric Softeners—Various through-the-wash fabric softeners, especiallythe impalpable smectite clays of U.S. Pat. No. 4,062,647, Storm andNirschl, issued Dec. 13, 1977, as well as other softener clays known inthe art, can optionally be used typically at levels of from about 0.5%to about 10% by weight in the present compositions to provide fabricsoftener benefits concurrently with fabric cleaning. Clay softeners canbe used in combination with amine and cationic softeners as disclosed,for.example, in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 andU.S. Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981. Moreover,in laundry cleaning methods herein, known fabric softeners, includingbiodegradable types, can be used in pretreat, mainwash, post-wash anddryer-added modes.

Perfumes—Perfumes and perfumery ingredients useful in the presentcompositions and processes comprise a wide variety of natural andsynthetic chemical ingredients, including, but not limited to,aldehydes, ketones, esters, and the like. Also included are variousnatural extracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes typically comprise from about 0.01%to about 2%, by weight, of the detergent compositions herein, andindividual perfumery ingredients can comprise from about 0.0001% toabout 90% of a finished perfume composition.

Non-limiting examples of perfume ingredients useful herein include:7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;ionone methyl; ionone gamma methyl; methyl cedrylone; methyldihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone;benzophenone; methyl beta-naphthyl ketone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal,4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecane; condensation products ofhydroxycitronellal and methyl anthranilate, condensation products ofhydroxycitronellal and indol, condensation products of phenylacetaldehyde and indol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin;decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acidlactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;beta-naphthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1b]furan; cedrol,5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenylacetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those that provide thelargest odor improvements in finished product compositions containingcellulases. These perfumes include but are not limited to: hexylcinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene;benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate;beta-napthol methyl ether; methyl beta-naphthyl ketone;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane;dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; anisaldehyde;coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resinsfrom a variety of sources including, but not limited to: Peru balsam,Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoinresin, coriander and lavandin. Still other perfume chemicals includephenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol,nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, andeugenol. Carriers such as diethylphthalate can be used in the finishedperfume compositions.

Other Detergent Ingredients—A wide variety of other ingredients usefulin detergent compositions can be included in the compositions herein,including other active ingredients, carriers, hydrotropes, processingaids, dyes or pigments, solvents for liquid formulations, solid fillersfor bar compositions, etc. If high sudsing is desired, suds boosterssuch as the C₁₀-C₁₆ alkanolamides can be incorporated into thecompositions, typically at 1%-10% levels. The C₁₀-C₁₄ monoethanol anddiethanol amides illustrate a typical class of such suds boosters. Useof such suds boosters with high sudsing adjunct surfactants such as theamine oxides, betaines and sultaines noted above is also advantageous.If desired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄ and the like, can be added at levels of, typically,0.1%-2%, to provide additional suds and to enhance grease removalperformance, especially for liquid dishwashing purposes.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.0 and 10.5, more preferably between about 7.0 to about 9.5. Liquiddishwashing product formulations preferably have a pH between about 6.8and about 9.0. Laundry products are typically at pH 9-11. Techniques forcontrolling pH at recommended usage levels include the use of buffers,alkalis, acids, etc., and are well known to those skilled in the art.

Conventional Skin Care Additives

The skin care compositions of the present invention may contain avariety of other ingredients such as are conventionally used in a givenproduct type provided they do not unacceptably alter the benefits of theinvention. These optional components should be suitable for applicationto human skin, that is, when incorporated into the composition they aresuitable for use in contact with human skin without undue toxicity,incompatibility, instability, allergic response, and the like within thescope of sound medical or formulator's judgment. The CTFA CosmeticIngredient Handbook, Second Edition (1992) describes a wide variety ofnonlimiting cosmetic and pharmaceutical ingredients commonly used in theskin care industry, which are suitable for use in the compositions ofthe present invention. Examples of these ingredient classes include:abrasives, absorbents, aesthetic components such as perfumes, pigments,colorings/colorants, essential oils, skin sensates, astringents, etc.(e.g., clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyllactate, witch hazel distillate), anti-acne agents (e.g., resorcinol,sulfur, salicylic acid, erythromycin, zinc, etc.), anti-caking agents,antifoaming agents, antimicrobial agents (e.g., iodopropylbutylcarbamate), antioxidants, binders, biological additives, bufferingagents, bulking agents, chelating agents, chemical additives, colorants,cosmetic astringents, cosmetic biocides, denaturants, drug astringents,external analgesics, film formers or materials, e.g., polymers, foraiding the film-forming properties and substantivity of the composition(e.g., copolymer of eicosene and vinyl pyrrolidone), humectants,opacifying agents, pH adjusters, propellants, reducing agents,sequestrants, skin bleaching agents (or lightening agents) (e.g.,hydroquinone, kojic acid, ascorbic acid, magnesium ascorbyl phosphate,ascorbyl glucosamine), skin-conditioning agents (humectants, includingmiscellaneous and occlusive), skin soothing and/or healing agents (e.g.,panthenol and derivatives (e.g., ethyl panthenol), aloe vera,pantothenic acid and its derivatives, allantoin, bisabolol, anddipotassium glycyrrhizinate), skin treating agents including agents forpreventing, retarding, arresting, and/or reversing skin wrinkles (e.g.,alpha-hydroxy acids such as lactic acid and glycolic acid andbeta-hydroxy acids such as salicylic acid), thickeners, and vitamins andderivatives thereof (e.g. tocopherol, tocopherol acetate, retinoic acid,retinol, retinoids, retinyl palmitate, niacin, niacinamide, and thelike).

The skin care compositions of the present invention may contain one ormore of such optional components. Preferred skin care compositionsoptionally contain one or more materials selected from UVB sunscreenactives, anti-acne actives, artificial tanning agents, humectants,moisturizers, skin conditioners, and thickening/structuring agents.

UVB Sunscreen Active

The skin care compositions of the present invention can comprise a UVBsunscreen active which absorbs UV radiation having a wavelength of fromabout 290 nm to about 320 nm. As used herein, the UVB sunscreen activemeans an active other than the dibenzoylmethane sunscreen active whichitself may possess UVB absorption properties. The skin care compositionsshould comprise an amount of the UVB active effective to provide UVBprotection either independently or in combination with other UVprotective actives which may be present in the skin care composition,preferably from about 0.1% to about 10%, more preferably from about 0.1%to about 4%, and most preferably from about 0.5% to about 2.5% by weightof the composition.

A wide variety of UVB sunscreen actives, including both organicsunscreen actives and inorganic physical sunblocks, are suitable for useherein. Nonlimiting examples of such sunscreen actives are described inU.S. Pat. No. 5,087,445 issued Feb. 11, 1992 to Haffey et al.; and U.S.Pat. Nos. 5,073,371 and 5,073,372, both issued on Dec. 17, 1991 toTurner et al. Nonlimiting examples of suitable physical sunblocks aredescribed in CTFA International Cosmetic Ingredient Dictionary, Sixthedition, 1995, pp. 1026-28, and 1103.

Preferred UVB sunscreen actives are selected from group consisting of2-phenyl-benzimidazole-5-sulfonic acid, octocrylene, TEA salicylate,octyl dimethyl PABA, zinc oxide, titanium dioxide, and mixtures thereof.A preferred organic sunscreen active is2-phenyl-benzimidazole-5-sulfonic acid while preferred inorganicphysical sunblocks are zinc oxide, titanium dioxide, and mixturesthereof. Salt and acid-neutralized forms of the acidic sunscreens arealso contemplated herein.

When used, the physical sunblocks are present in an amount such that thepresent skin care compositions are transparent on the skin (i.e.,non-whitening), preferably less than or equal to about 5%. When titaniumdioxide is used, it can have an anatase, rutile, or amorphous structure.Physical sunblock particles, e.g., titanium dioxide and zinc oxide, canbe uncoated or coated with a variety of materials including, but notlimited to, amino acids; aluminum compounds such as alumina, aluminumstearate, aluminum laurate, and the like; carboxylic acids and theirsalts, e.g., stearic acid and its salts; phospholipids such as lecithin;organic silicone compounds; inorganic silicone compounds such as silicaand silicates; and mixtures thereof. A preferred titanium dioxide iscommercially available from Tayca (Japan) and is distributed by Tri-KIndustries (Emerson, N.J.) under the MT micronized series (e.g., MT100SAS).

Anti-Acne Actives

The skin care compositions of the present invention may comprise one ormore anti-acne actives. Examples of useful anti-acne actives aredescribed in further detail in U.S. Pat. No. 5,607,980, issued to McAteeet al., on Mar. 4, 1997.

Artificial Tanning Agents

The skin care compositions of the present invention can comprise one ormore artificial tanning agents. Suitable tanning agents includedihydroxyacetone, tyrosine, tyrosine esters and phopho-pho-DOPA. See TheMerck Index, Tenth Edition, entry 3167, p. 463 (1983), and“Dihydroxyacetone for Cosmetics”, E. Merck Technical Bulletin, 03-304110, 319 897, 180 588.

Structuring Agent

The skin care compositions of the present invention may contain astructuring agent. Structuring agents are particularly preferred in theoil-in-water emulsions of the present invention. Without being limitedby theory, it is believed that the structuring agent assists inproviding rheological characteristics to the skin care composition whichcontribute to the stability of the composition. For example, thestructuring agent tends to assist in the formation of the liquidcrystalline gel network structures. The structuring agent may alsofunction as an emulsifier or surfactant. Preferred skin carecompositions of this invention comprise from about 0.5% to about 20%,more preferably from about 1% to about 10%, most preferably from about1% to about 5%, of one or more structuring agents.

The preferred structuring agents for use in the skin care compositionsof the present invention are selected from the group consisting ofstearic acid, palmitic acid, stearyl alcohol, cetyl alcohol, behenylalcohol, stearic acid, palmitic acid, the polyethylene glycol ether ofstearyl alcohol having an average of about 1 to about 21 ethylene oxideunits, the polyethylene glycol ether of cetyl alcohol having an averageof about 1 to about 5 ethylene oxide units, and mixtures thereof. Morepreferred structuring agents for use in the skin care compositions ofthe present invention are selected from the group consisting of stearylalcohol, cetyl alcohol, behenyl alcohol, the polyethylene glycol etherof stearyl alcohol having an average of about 2 ethylene oxide units(steareth-2), the polyethylene glycol ether of stearyl alcohol having anaverage of about 21 ethylene oxide units (steareth-21), the polyethyleneglycol ether of cetyl alcohol having an average of about 2 ethyleneoxide units, and mixtures thereof. Even more preferred structuringagents are selected from the group consisting of stearic acid, palmiticacid, stearyl alcohol, cetyl alcohol, behenyl alcohol, steareth-2,steareth-21, and mixtures thereof.

Thickening Agent (Including Thickeners and Gelling Agents)

The skin care compositions of the present invention can comprise one ormore thickening agents, preferably from about 0.1% to about 5%, morepreferably from about 0.1% to about 3%, and most preferably from about0.25% to about 2%, by weight of the composition.

Nonlimiting classes of thickening agents include those selected from thegroup consisting of:

Carboxylic Acid Polymers—These polymers are crosslinked compoundscontaining one or more monomers derived from acrylic acid, substitutedacrylic acids, and salts and esters of these acrylic acids and thesubstituted acrylic acids, wherein the crosslinking agent contains twoor more carbon-carbon double bonds and is derived from a polyhydricalcohol. Polymers useful in the present invention are more fullydescribed in U.S. Pat. No. 5,087,445, to Haffey et al., issued Feb. 11,1992; U.S. Pat. No. 4,509,949, to Huang et al., issued Apr. 5, 1985;U.S. Pat. No. 2,798,053, to Brown, issued Jul. 2, 1957; and in CTFAInternational Cosmetic Ingredient Dictionary, Fourth edition, 1991, pp.12 and 80.

Examples of commercially available carboxylic acid polymers usefulherein include the carbomers, which are homopolymers of acrylic acidcrosslinked with allyl ethers of sucrose or pentaerytritol. Thecarbomers are available as the Carbopol® 900 series from B.F. Goodrich(e.g., Carbopol® 954). In addition, other suitable carboxylic acidpolymeric agents include copolymers of C₁₀₋₃₀ alkyl acrylates with oneor more monomers of acrylic acid, methacrylic acid, or one of theirshort chain (i.e. C₁₋₄ alcohol) esters, wherein the crosslinking agentis an allyl ether of sucrose or pentaerytritol. These copolymers areknown as acrylates/C₁₀₋₃₀ alkyl acrylate crosspolymers and arecommercially available as Carbopol® 1342, Carbopol® 1382, Pemulen TR-1,and Pemulen TR-2, from B.F. Goodrich. In other words, examples ofcarboxylic acid polymer thickeners useful herein are those selected fromthe group consisting of carbomers, acrylates/C₁₀-C₃₀ alkyl acrylatecrosspolymers, and mixtures thereof.

Crosslinked Polyacrylate Polymers—The skin care compositions of thepresent invention can optionally comprise crosslinked polyacrylatepolymers useful as thickeners or gelling agents including both cationicand nonionic polymers, with the cationics being generally preferred.Examples of useful crosslinked nonionic polyacrylate polymers andcrosslinked cationic polyacrylate polymers are those described in U.S.Pat. No. 5,100,660, to Hawe et al., issued Mar. 31, 1992; U.S. Pat. No.4,849,484, to Heard, issued Jul. 18, 1989; U.S. Pat. No. 4,835,206, toFarrar et al., issued May 30, 1989; U.S. Pat. No. 4,628,078 to Glover etal. issued Dec. 9, 1986; U.S. Pat. No. 4,599,379 to Flesher et al.issued Jul. 8, 1986; and EP 228,868, to Farrar et al., published Jul.15, 1987.

Polyacrylamide Polymers—The skin care compositions of the presentinvention can optionally comprise polyacrylamide polymers, especiallynonionic polyacrylamide polymers including substituted branched orunbranched polymers. Most preferred among these polyacrylamide polymersis the nonionic polymer given the CTFA designation polyacrylamide andisoparaffin and laureth-7, available under the Tradename Sepigel 305from Seppic Corporation (Fairfield, N.J.).

Other polyacrylamide polymers useful herein include multi-blockcopolymers of acrylamides and substituted acrylamides with acrylic acidsand substituted acrylic acids. Commercially available examples of thesemulti-block copolymers include Hypan SR150H, SS500V, SS500W, SSSA100H,from Lipo Chemicals, Inc., (Patterson, N.J.).

Polysaccharides—A wide variety of polysaccharides are useful herein.“Polysaccharides” refer to gelling agents which contain a backbone ofrepeating sugar (i.e. carbohydrate) units. Nonlimiting examples ofpolysaccharide gelling agents include those selected from the groupconsisting of cellulose, carboxymethyl hydroxyethylcellulose, celluloseacetate propionate carboxylate, hydroxyethylcellulose, hydroxyethylethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose,methyl hydroxyethylcellulose, microcrystalline cellulose, sodiumcellulose sulfate, and mixtures thereof. Also useful herein are thealkyl substituted celluloses. In these polymers, the hydroxy groups ofthe cellulose polymer is hydroxyalkylated (preferably hydroxyethylatedor hydroxypropylated) to form a hydroxyalkylated cellulose which is thenfurther modified with a C₁₀-C₃₀ straight chain or branched chain alkylgroup through an ether linkage. Typically these polymers are ethers ofC₁₀-C₃₀ straight or branched chain alcohols with hydroxyalkylcelluloses.Examples of alkyl groups useful herein include those selected from thegroup consisting of stearyl, isostearyl, lauryl, myristyl, cetyl,isocetyl, cocoyl (i.e. alkyl groups derived from the alcohols of coconutoil), palmityl, oleyl, linoleyl, linolenyl, ricinoleyl, behenyl, andmixtures thereof. Preferred among the alkyl hydroxyalkyl celluloseethers is the material given the CTFA designation cetylhydroxyethylcellulose, which is the ether of cetyl alcohol andhydroxyethylcellulose. This material is sold under the tradenameNatrosol® CS Plus from Aqualon Corporation (Wilmington, Del.).

Other useful polysaccharides include scleroglucans comprising a linearchain of (1-3) linked glucose units with a (1-6) linked glucose everythree units, a commercially available example of which is Clearogel™CS11 from Michel Mercier Products Inc. (Mountainside, N.J.).

Gums—Other thickening and gelling agents useful herein include materialswhich are primarily derived from natural sources. Nonlimiting examplesof these gelling agent gums include materials selected from the groupconsisting of acacia, agar, algin, alginic acid, ammonium alginate,amylopectin, calcium alginate, calcium carrageenan, camitine,carrageenan, dextrin, gelatin, gellan gum, guar gum, guarhydroxypropyltrimonium chloride, hectorite, hyaluroinic acid, hydratedsilica, hydroxypropyl chitosan, hydroxypropyl guar, karaya gum, kelp,locust bean gum, natto gum, potassium alginate, potassium carrageenan,propylene glycol alginate, sclerotium gum, sodium carboxymethyl dextran,sodium carrageenan, tragacanth gum, xanthan gum, and mixtures thereof.

Preferred skin care compositions of the present invention include athickening agent selected from the group consisting of carboxylic acidpolymers, crosslinked polyacrylate polymers, polyacrylamide polymers,and mixtures thereof, more preferably selected from the group consistingof carboxylic acid polymers, polyacrylamide polymers, and mixturesthereof.

Humectants, Moisturizers, and Skin Conditioners

Preferred skin care compositions optionally comprise one or morehumectants, moisturizers, or skin conditioners. A variety of thesematerials can be employed and each can be present at a level of fromabout 0.01% to about 20%, more preferably from about 0.1% to about 10%,and most preferably from about 0.5% to about 7%. These materialsinclude, but are not limited to, guanidine; glycolic acid and glycolate.salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid andlactate salts (e.g. ammonium and quaternary alkyl ammonium); aloe verain any of its variety of forms (e.g., aloe vera gel); polyhydroxyalcohols such as sorbitol, glycerol, hexanetriol, propylene glycol,butylene glycol, hexylene glycol and the like; polyethylene glycols;sugars and starches; sugar and starch derivatives (e.g., alkoxylatedglucose); hyaluronic acid; lactamide monoethanolamine; acetamidemonoethanolamine; and mixtures thereof. Also useful herein are thepropoxylated glycerols described in U.S. Pat. No. 4,976,953, to Orr etal., issued Dec. 11, 1990.

Also useful are various C₁-C₃₀ monoesters and polyesters of sugars andrelated materials. These esters are derived from a sugar or polyolmoiety and one or more carboxylic acid moieties. Such ester materialsare further described in, U.S. Pat. No. 2,831,854, U.S. Pat. No.4,005,196, to Jandacek, issued Jan. 25, 1977; U.S. Pat. No. 4,005,195,to Jandacek, issued Jan. 25, 1977, U.S. Pat. No. 5,306,516, to Letton etal., issued Apr. 26, 1994; U.S. Pat. No. 5,306,515, to Letton et al.,issued Apr. 26, 1994; U.S. Pat. No. 5,305,514, to Letton et al., issuedApr. 26, 1994; U.S. Pat. No. 4,797,300, to Jandacek et al., issued Jan.10, 1989; U.S. Pat. No. 3,963,699, to Rizzi et al, issued Jun. 15, 1976;U.S. Pat. No. 4,518,772, to Volpenhein, issued May 21, 1985; and U.S.Pat. No. 4,517,360, to Volpenhein, issued May 21, 1985.

Emulsifiers

The skin care compositions of the present invention can also compriseone or more emulsifiers. Emulsifiers generally serve to reduce the ininterfacial tension between phases and improve the formulation andstability of an emulsion. Suitable emulsifiers include a wide variety ofnonionic, cationic, anionic, and zwitterionic emulsifiers. SeeMcCutcheon's, Detergents and Emulsifiers, North American Edition (1986),published by Allured Publishing Corporation; U.S. Pat. No. 5,011,681issued to Ciotti et al. on Apr. 30, 1991; U.S. Pat. No. 4,421,769 issuedto Dixon et al. on Dec. 20, 1983; and U.S. Pat. No. 3,755,560 issued toDickert et al. on Aug. 28, 1973.

Suitable emulsifier types include esters of glycerin, esters ofpropylene glycol, fatty acid esters of polyethylene glycol, fatty acidesters of polypropylene glycol, esters of sorbitol, esters of sorbitananhydrides, carboxylic acid copolymers, esters and ethers of glucose,ethoxylated ethers, ethoxylated alcohols, alkyl phosphates,polyoxyethylene fatty ether phosphates, fatty acid amides, acyllactylates, soaps and mixtures thereof.

Suitable emulsifiers can include, but are not limited to, TEA stearate,DEA oleth-3 phosphate, polyethylene glycol 20 sorbitan monolaurate(polysorbate 20), polyethylene glycol 5 soya sterol, steareth-2,steareth-20, steareth-21, ceteareth-20, PPG-2 methyl glucose etherdistearate, ceteth-10, polysorbate 80, cetyl phosphate, potassium cetylphosphate, diethanolamine cetyl phosphate, polysorbate 60, glycerylstearate, PEG-100 stearate, and mixtures thereof. Preferred emulsifiersare steareth-2, steareth-21, TEA stearate, diethanolamine cetylphosphate, potassium cetyl phosphate, and mixtures thereof. Theemulsifier can be used individually or as a mixture of two or more andcomprises from about 0.1% to about 10%, more preferably from about 0.15%to about 7%, and most preferably from about 0.25% to about 5% of thecompositions of the present invention.

Conventional Personal Cleansing Additive

These are additives which are conventionally used in personal cleansingcompositions, such as toilet soaps, body washes, shampoos and medicatedwipes. Examples of these are conditioning agents, conventional personalcare polymer, antidandruff agent, surfactant; and mixtures thereof.These conventional personal cleansing additives are just some of thepossible ingredients which can be conventionally added to personalcleansing compositions.

The conditioning agents, useful in the present invention can be furtherselected from the group comprising non-volatile hydrocarbonsconditioning agents, silicone conditioning agents and mixtures thereof.

The conventional personal care polymers useful in the present inventioncan be further selected from the group comprising deposition polymers,styling polymers and solvent, dispersed phase polymers, and mixturesthereof.

The personal cleansing compositions of the present invention is in theform of a liquid or a liquid gel. It can contain for example, suspendedingredients, more than one phase etc. Effectively the personal cleansingcompositions of the present invention can be in the form of any type ofliquid or liquid gel and contain any additive conventionally added topersonal cleansing compositions, such as shampoos, body wash gels, bathgels etc.

For more information and additional examples of conventional personalcleansing additives see WO 99/18928 and WO 99/18929, both assigned toProcter & Gamble.

Suitable conventional personal cleansing additives include anti staticagents, dyes, diluents, emollient oils (such as polyisobutylene, mineraloil, petrolatum and isocetyl stearyl stearate), pearlescent aids, foamboosters, styling polymer, pediculocides, dispersed phase polymers,hydrotropes, hair or skin conditioning agents such as nonvolatilesilicone conditioning agents and nonvolatile organic conditioningagents, solvent pH adjusting agents, perfumes, preservatives, lowviscosity surfactant soluble conditioning oil, electrolytes,amphiphiles, proteins, phase separation initiator, cationic spreadingagents, such as cationic surfactants, antioxidants; chelators andsequestrants, surfactants, antidandruff agent such as plateletpyridinethione salt crystal, sulfur, octopirox, selenium sulfide,ketoconazole and pyridinethione salts, organic deposition polymers andaesthetic components such as fragrances, colorings, essential oils, skinsensates, astringents, suspending agent skin soothing agents, aqueousliquid carrier, skin healing agents and the like, nonlimiting examplesof these aesthetic components include panthenol and derivatives (e.g.ethyl panthenol), pantothenic acid and its derivatives, clove oil,menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazeldistillate, allantoin, (?)bisabolol, dipotassium glycyrrhizinate and thelike, sunscreens, thickeners, vitamins and derivatives thereof (e.g.,ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol,retinoids, and the like), and viscosity adjusting agents. This list ofconventional personal cleansing additives is not meant to be exclusive,and other conventional personal cleansing additives can be used.

For more information and additional examples of conditioning agents seeWO 98/16189 and WO 98/18433. See also U.S. Pat. No. 4,741,855. All threeof these references are incorporated herein by reference.

Suitable suspending agents are described in U.S. Pat. Nos. 4,741,855,4,788,006, 2,798,053, and 4,704,272, which description is incorporatedherein by reference.

For suitable deposition polymers see WO 02/22091, WO 98/18433, and WO99/05243, all of which are incorporated herein by reference.

See WO 98/18434 and WO 99/05243, both of which are incorporated hereinby reference.

Examples of some suitable styling polymers are described in U.S. Pat.No. 5,120,531, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,120,532, to Wells et al., issued Jun. 9, 1992; U.S. Pat. No.5,104,642, to Wells et al., issued Apr. 14, 1992; U.S. Pat. No.4,272,511, to Papantoniou et al., issued Jun. 9, 1981; U.S. Pat. No.4,963,348, to Bolich et al., issued Oct. 16, 1990, EPO Application90307528.1, published as EPO Application 0 408 311 A2 on Jan. 11, 1991,Hayama, et al.; U.S. Pat. No. 5,061,481, issued Oct. 29, 1991, Suzuki etal.; U.S. Pat. No. 5,106,609, Bolich et al., issued Apr. 21, 1992; U.S.Pat. No. 5,100,658, Bolich et al., issued Mar. 31, 1992; U.S. Pat. No.5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992; U.S. Pat. No.5,104,646, Bolich et al., issued Apr. 14, 1992; U.S. Pat. No. 5,658,557,Torgerson et al., filed Aug. 27, 1991, and U.S. Pat. No. 4,196,190, toGehman et al., issued Apr. 1, 1980, which descriptions are incorporatedherein by reference.

For suitable dispersed phase polymer see also U.S. Pat. No. 5,783,200,which is incorporated herein by reference.

For suitable phase separation initiators see WO 98/29080 and WO99/18929, both assigned to Procter & Gamble.

For suitable antidandruff agent see also U.S. Pat. No. 4,948,576 toVerdicohio et al, and WO 98/18434, WO 97/35548, WO 97/26854. U.S. Pat.Nos. 4,379,753, 2,694,668, 3,152,046, 4,089,945, 4,885,107, 2,809,971,3,236,733, 3,753,196, 3,761,418, 4,345,080, 4,323,683, 4,379,753 and4,470,982 all of which are incorporated herein by reference.

Optional Fabric Softener Ingredients

The fabric softening composition of the invention can also containoptional ingredients. A comprehensive list of possible optionalingredients can be found in U.S. Pat. No. 5,747,443, which isincorporated herein by reference.

Low molecular weight water soluble solvents—can also be used at levelsof from 0% to about 12%, preferably from about 1% to about 10%, morepreferably from about 2% to about 8%. The water soluble solvents cannotprovide a clear product at the same low levels of the principal solventsdescribed hereinbefore but can provide clear product when the principalsolvent is not sufficient to provide completely clear product. Thepresence of these water soluble solvents is therefore highly desirable.Such solvents include: ethanol; isopropanol; 1,2-propanediol;1,3-propanediol; propylene carbonate; etc. but do not include any of theprincipal solvents (B). These water soluble solvents have a greateraffinity for water in the presence of hydrophobic materials like thesoftener active than the principal solvents.

Brighteners—The fabric softening compositions herein can also optionallycontain from about 0.005% to 5% by weight of certain types ofhydrophilic optical brighteners which also provide a dye transferinhibition action. If used, the compositions herein will preferablycomprise from about 0.001% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention arethose having the structural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the rinse added compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.

Dispersibility Aids

Optional Viscosity/Dispersibility Modifiers—Relatively concentratedfabric softening compositions containing both saturated and unsaturateddiester quaternary ammonium compounds can be prepared that are stablewithout the addition of concentration aids. However, the fabricsoftening compositions of the present invention may require organicand/or inorganic concentration aids to go to even higher concentrationsand/or to meet higher stability standards depending on the otheringredients. These concentration aids which typically can be viscositymodifiers may be needed, or preferred, for ensuring stability underextreme conditions when particular softener active levels are used. Thesurfactant concentration aids are typically selected from the groupconsisting of (1) single long chain alkyl cationic surfactants; (2)nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5)mixtures thereof. These aids are described in U.S. Pat. No. 5,545,340,specifically on page 14, line 12 to page 20, line 12, which is hereinincorporated by reference.

When said dispersibility aids are present, the total level is from about2% to about 25%, preferably from about 3% to about 17%, more preferablyfrom about 4% to about 15%, and even more preferably from 5% to about13% by weight of the composition. These materials can either be added aspart of the active softener raw material e.g., the mono-long chain alkylcationic surfactant and/or the fatty acid which are reactants used toform the biodegradable fabric softener active as discussed hereinbefore,or added as a separate component.

Mono-Alkyl Cationic Quaternary Ammonium Compound—When the mono-alkylcationic quaternary ammonium compound is present, it is typicallypresent at a level of from about 2% to about 25%, preferably from about3% to about 17%, more preferably from about 4% to about 15%, and evenmore preferably from 5% to about 13% by weight of the composition, thetotal mono-alkyl cationic quaternary ammonium compound being at least atan effective level.

Such mono-alkyl cationic quaternary ammonium compounds useful in thepresent invention are, preferably, quaternary ammonium salts of thegeneral formula:

[R⁴N⁺(R⁵)₃]X⁻

wherein R⁴ is C₈-C₂₂ alkyl or alkenyl group, preferably C₁₀-C₁₈ alkyl oralkenyl group; more preferably C₁₀-C₁₄ or C₁₆-C₁₈ alkyl or alkenylgroup; each R⁵ is a C₁-C₆ alkyl or substituted alkyl group (e.g.,hydroxy alkyl), preferably C₁-C₃ alkyl group, e.g., methyl (mostpreferred), ethyl, propyl, and the like, a benzyl group, hydrogen, apolyethoxylated chain with from about 2 to about 20 oxyethylene units,preferably from about 2.5 to about 13 oxyethylene units, more preferablyfrom about 3 to about 10 oxyethylene units, and mixtures thereof, and X⁻is as defined hereinbefore.

Especially preferred dispersibility aids are monolauryl trimethylammonium chloride and monotallow trimethyl ammonium chloride availablefrom Witco under the trade name Varisoft® 471 and monooleyl trimethylammonium chloride available from Witco under the tradename Varisoft®417.

The R⁴ group can also be attached to the cationic nitrogen atom througha group containing one, or more, ester, amide, ether, amine, etc.,linking groups which can be desirable for increased concentratability offabric softening compositions components. Such linking groups arepreferably within from about one to about three carbon atoms of thenitrogen atom.

Mono-alkyl cationic quaternary ammonium compounds also include C₈-C₂₂alkyl choline esters. The preferred dispersibility aids of this typehave the formula:

R¹C(O)—O—CH₂CH₂N⁺(R)₃X⁻

wherein R¹, R and X⁻ are as defined previously.

Highly preferred dispersibility aids include C₁₂-C₁₄ coco choline esterand C₁₆-C₁₈ tallow choline ester.

Suitable biodegradable single-long-chain alkyl dispersibility aidscontaining an ester linkage in the long chains are described in U.S.Pat. No. 4,840,738, Hardy and Walley, issued Jun. 20, 1989, said patentbeing incorporated herein by reference.

When the dispersibility aid comprises alkyl choline esters, preferablythe compositions also contain a small amount, preferably from about 2%to about 5% by weight of the composition, of organic acid. Organic acidsare described in European Patent Application No. 404,471, Machin et al.,published on Dec. 27, 1990, supra, which is herein incorporated byreference. Preferably the organic acid is selected from the groupconsisting of glycolic acid, acetic acid, citric acid, and mixturesthereof.

Ethoxylated quaternary ammonium compounds which can serve as thedispersibility aid include ethylbis(polyethoxy ethanol)alkylammoniumethyl-sulfate with 17 moles of ethylene oxide, available under the tradename Variquat® 66 from Sherex Chemical Company; polyethylene glycol (15)oleammonium chloride, available under the trade name Ethoquad® 0/25 fromAkzo; and polyethylene glycol (15) cocomonium chloride, available underthe trade name Ethoquad® C/25 from Akzo.

Although the main function of the dispersibility aid is to increase thedispersibility of the ester softener, preferably the dispersibility aidsof the present invention also have some softening properties to boostsoftening performance of the composition. Therefore, preferably thecompositions of the present. invention are essentially free ofnon-nitrogenous ethoxylated nonionic dispersibility aids which willdecrease the overall softening performance of the compositions.

Also, quaternary compounds having only a single long alkyl chain, canprotect the cationic softener from interacting with anionic surfactantsand/or detergent builders that are carried over into the rinse from thewash solution.

Amine Oxides—Suitable amine oxides include those with one alkyl orhydroxyalkyl moiety of about 8 to about 22 carbon atoms, preferably fromabout 10 to about 18 carbon atoms, more preferably from about 8 to about14 carbon atoms, and two alkyl moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups with about 1 to about3 carbon atoms.

Examples include dimethyloctylamine oxide, diethyldecylarnine oxide,bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide,dipropyl-tetradecylamine oxide, methylethylhexadecylamine oxide,dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyldimethylamine oxide.

Stabilizers—Stabilizers can be present in the fabric softeningcompositions of the present invention. The term “stabilizer,” as usedherein, includes antioxidants and reductive agents. These agents arepresent at a level of from 0% to about 2%, preferably from about 0.01%to about 0.2%, more preferably from about 0.035% to about 0.1% forantioxidants, and more preferably from about 0.01% to about 0.2% forreductive agents. These assure good odor stability under long termstorage conditions. Antioxidants and reductive agent stabilizers areespecially critical for unscented or low scent products (no or lowperfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox® S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox®-6; butylated hydroxytoluene, available from UOPProcess Division under the trade name Sustane® BHT; tertiarybutylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ;natural tocopherols, Eastman Chemical Products, Inc., as Tenox®GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,Inc., as BHA; long chain esters (C8-C22) of gallic acid, e.g., dodecylgallate; Irganox® 1010; Irganox® 1035; Irganox® B 1171; Irganox® 1425;Irganox® 3114; Irganox® 3125; and mixtures thereof; preferably Irganox®3125, Irganox® 1425, Irganox® 3114, and mixtures thereof; morepreferably Irganox® 3125 alone or mixed with citric acid and/or otherchelators such as isopropyl citrate, Dequest® 2010, available fromMonsanto with a chemical name of 1-hydroxyethylidene-1,1-diphosphonicacid (etidronic acid), and Tiron®, available from Kodak with a chemicalname of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®,available from Aldrich with a chemical name ofdiethylenetriaminepentaacetic acid.

Soil Release Agent—In the present fabric softening compositions, anoptional soil release agent can be added. The addition of the soilrelease agent can occur in combination with the premix, in combinationwith the acid/water seat, before or after electrolyte addition, or afterthe final composition is made. The softening composition prepared by theprocess of the present invention herein can contain from 0% to about10%, preferably from 0.2% to about 5%, of a soil release agent. Suitablesoil release agents are described hereinbefore.

Examples of suitable soil release agents include the commerciallyavailable materials Zelcon 4780® (from Dupont) and Milease T® (fromICI).

A more complete disclosure of soil release agents is contained in U.S.Pat. No.: 4,661,267, Decker, Konig, Straathof, and Gosselink, issuedApr. 28, 1987; U.S. Pat. No. 4,711,730, Gosselink and Diehl, issued Dec.8, 1987; U.S. Pat. No. 4,749,596, Evans, Huntington, Stewart, Wolf, andZimmerer, issued Jun. 7, 1988; U.S. Pat. No. 4,818,569, Trinh,Gosselink, and Rattinger, issued Apr. 4, 1989; U.S. Pat. No. 4,877,896,Maldonado, Trinh, and Gosselink, issued Oct. 31, 1989; U.S. Pat. No.4,956,447, Gosselink et al., issues Sep. 11, 1990; and U.S. Pat. No.4,976,879, Maldonado, Trinh, and Gosselink, issued Dec. 11, 1990, all ofsaid patents being incorporated herein by reference.

These soil release agents can also act as scum dispersants.

Scum Dispersant—In the present invention, the premix can be combinedwith an optional scum dispersant, other than the soil release agent, andheated to a temperature at or above the melting point(s) of thecomponents.

The preferred scum dispersants herein are formed by highly ethoxylatinghydrophobic materials. The hydrophobic material can be a fatty alcohol,fatty acid, fatty amine, fatty acid amide, amine oxide, quaternaryammonium compound, or the hydrophobic moieties used to form soil releasepolymers. The preferred scum dispersants are highly ethoxylated, e.g.,more than about 17, preferably more than about 25, more preferably morethan about 40, moles of ethylene oxide per molecule on the average, withthe polyethylene oxide portion being from about 76% to about 97%,preferably from about 81% to about 94%, of the total molecular weight.

The level of scum dispersant is sufficient to keep the scum at anacceptable, preferably unnoticeable to the consumer, level under theconditions of use, but not enough to adversely affect softening. Forsome purposes it is desirable that the scum is nonexistent. Depending onthe amount of anionic or nonionic detergent, etc., used in the washcycle of a typical laundering process, the efficiency of the rinsingsteps prior to the introduction of the compositions herein, and thewater hardness, the amount of anionic or nonionic detergent surfactantand detergency builder (especially phosphates and zeolites) entrapped inthe fabric (laundry) will vary. Normally, the minimum amount of scumdispersant should be used to avoid adversely affecting softeningproperties. Typically scum dispersion requires at least about 2%,preferably at least about 4% (at least 6% and preferably at least 10%for maximum scum avoidance) based upon the level of softener active.However, at levels of about 10% (relative to the softener material) ormore, one risks loss of softening efficacy of the product especiallywhen the fabrics contain high proportions of nonionic surfactant whichhas been absorbed during the washing operation.

Preferred scum dispersants are: Brij 700®; Varonic U-250®; GenapolT-500®, Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.

Bactericides—Examples of bactericides used in the compositions of thisinvention include glutaraldehyde, formaldehyde,2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located inPhiladelphia, Pa., under the trade name Bronopol®, and a mixture of5-chloro-2-methyl-4-isothiazoline-3-one and2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under thetrade name Kathon about 1 to about 1,000 ppm by weight of the agent.

Perfume—The present invention can contain any softener compatibleperfume. Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138,Bacon et al., issued Mar. 19, 1996, said patent being incorporatedherein by reference.

As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants),. artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds. Other suitable perfumes are described hereinbefore.

Examples of perfume ingredients useful in the perfumes of the presentinvention compositions include, but are not limited to, hexyl cinnamicaldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate;terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol;2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol;3,7-dimethyl-trans-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol;3,7-dimethyl-1-octanol;2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde;tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

Additional examples of fragrance materials include, but are not limitedto, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil;dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate;beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;Schiff's base of4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methylanthranilate; cyclic ethyleneglycol diester of tridecandioic acid;3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;ionone beta; petitgrain; methyl cedrylone;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;16-hydroxy-9-hexadecenoic acid lactone;1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol;5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexylacetate; patchouli; olibanum resinoid; labdanum; vetivert; copaibabalsam; fir balsam; and condensation products of: hydroxycitronellal andmethyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehydeand indol; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1-carboxaldehydeand methyl anthranilate.

More examples of perfume components are geraniol; geranyl acetate;linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellylacetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol;terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethylacetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzylbenzoate; styrallyl acetate; dimethylbenzylcarbinol;trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononylacetate; vetiveryl acetate; vetiverol;2-methyl-3-(p-tert-butylphenyl)-propanal;2-methyl-3-(p-isopropylphenyl)-propanal;3-(p-tert-butylphenyl)-propanal;4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone; n-decanal;n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehydedimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedrylmethylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methylionones; isomethyl ionones; irones; cis-3-hexenol and esters thereof;indane musk fragrances; tetralin musk fragrances; isochroman muskfragrances; macrocyclic ketones; macrolactone musk fragrances; ethylenebrassylate.

The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

Perfume can be present at a level of from 0% to about 10%, preferablyfrom about 0.1% to about 5%, and more preferably from about 0.2% toabout 3%, by weight of the finished composition. Fabric softenercompositions of the present invention provide improved fabric perfumedeposition.

Chelating Agents—The compositions and processes herein can optionallyemploy one or more copper and/or nickel chelating agents (“chelators”).Such water-soluble chelating agents can be selected from the groupconsisting of amino carboxylates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof, all as hereinafter defined. The whiteness and/or brightness offabrics are substantially improved or restored by such chelating agentsand the stability of the materials in the compositions are improved.Suitable chelating agents are described hereinbefore.

Amino carboxylates useful as chelating agents herein includeethylenediaminetetraacetates (EDTA),N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA),ethylenediamine tetraproprionates, ethylenediamine-N,N′-diglutamates,2-hyroxhypropylenediamine-N,N′-disuccinates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates(DETPA), and ethanoldiglycines, including their water-soluble salts suchas the alkali metal, ammonium, and substituted ammonium salts thereofand mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates),diethylenetriamine-N,N,N′,N″,N″-pentakis(methane phosphonate) (DETMP)and 1-hydroxyethane-1,1-diphosphonate (HEDP). Preferably, these aminophosphonates to not contain alkyl or alkenyl groups with more than about6 carbon atoms.

The chelating agents are typically used in the present rinse process atlevels from about 2 ppm to about 25 ppm, for periods from 1 minute up toseveral hours' soaking.

The preferred EDDS chelator used herein (also known asethylenediamine-N,N′-disuccinate) is the material described in U.S. Pat.No. 4,704,233, cited hereinabove.

As can be seen from the foregoing, a wide variety of chelators can beused herein. Indeed, simple polycarboxylates such as citrate,oxydisuccinate, and the like, can also be used, although such chelatorsare not as effective as the amino carboxylates and phosphonates, on aweight basis. Accordingly, usage levels may be adjusted to take intoaccount differing degrees of chelating effectiveness. The chelatorsherein will preferably have a stability constant (of the fully ionizedchelator) for copper ions of at least about 5, preferably at least about7. Typically, the chelators will comprise from about 0.5% to about 10%,more preferably from about 0.75% to about 5%, by weight of thecompositions herein. Preferred chelators include DETMP, DETPA, NTA, EDDSand mixtures thereof.

Other Optional Ingredients—The present invention can include optionalcomponents conventionally used in textile treatment compositions, forexample: colorants; preservatives; surfactants; anti-shrinkage agents;fabric crisping agents; spotting agents; germicides; fungicides;anti-oxidants such as butylated hydroxy toluene, anti-corrosion agents,and the like.

Particularly preferred ingredients include water soluble calcium and/ormagnesium compounds, which provide additional stability. The chloridesalts are preferred, but acetate, nitrate, etc. salts can be used. Thelevel of said calcium and/or magnesium salts is from 0% to about 2%,preferably from about 0.05% to about 0.5%, more preferably from about0.1% to about 0.25%.

The present invention can also include other compatible ingredients,including those as disclosed in WO 96/21714, WO 96/21715, and WO96/02490, incorporated herein by reference.

Form of the Cleaning Compositions

The cleaning compositions in accordance with the invention can take avariety of physical forms including granular, gel, tablet, bar, paste,cream and liquid forms. The form can be dependent upon the end use ofthe composition. The compositions include the so-called concentratedgranular detergent compositions adapted to be added to a washing machineby means of a dispensing device placed in the machine drum with thesoiled fabric load.

The mean particle size of the components of granular compositions inaccordance with the invention should preferably be such that no morethat 5% of particles are greater than 1.7 mm in diameter and not morethan 5% of particles are less than 0.15 mm in diameter.

The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of Tyler sieves. The weight fractions therebyobtained are plotted against the aperture size of the sieves. The meanparticle size is taken to be the aperture size through which 50% byweight of the sample would pass.

Certain preferred granular detergent compositions in accordance with thepresent invention are the high-density types, now common in themarketplace; these typically have a bulk density of at least 600g/liter, more preferably from 650 g/liter to 1200 g/liter.

Surfactant Agglomerate Particles

One of the preferred methods of delivering surfactant in consumerproducts is to make surfactant agglomerate particles, which may take theform of flakes, prills, marumes, noodles, ribbons, but preferably takethe form of granules. A preferred way to process the particles is byagglomerating powders (e.g. aluminosilicate, carbonate) with high activesurfactant pastes and to control the particle size of the resultantagglomerates within specified limits. Such a process involves mixing aneffective amount of powder with a high active surfactant paste in one ormore agglomerators such as a pan agglomerator, a Z-blade mixer or morepreferably an in-line mixer such as those manufactured by Schugi(Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, andGebruder Lödige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used,such as a Lödige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95% byweight, preferably 70% by weight to 85% by weight of surfactant istypically used. The paste may be pumped into the agglomerator at atemperature high enough to maintain a pumpable viscosity, but low enoughto avoid degradation of the anionic surfactants used. An operatingtemperature of the paste of 50° C. to 80° C. is typical.

Laundry Washing Method

Machine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. By an effectiveamount of the detergent composition it is here meant from 40 g to 300 gof product dissolved or dispersed in a wash solution of volume from 5 to65 liters, as are typical product dosages and wash solution volumescommonly employed in conventional machine laundry methods.

As noted, surfactants are used herein in detergent compositions,preferably in combination with other detersive surfactants, at levelswhich are effective for achieving at least a directional improvement incleaning performance. In the context of a fabric laundry composition,such “usage levels” can vary widely, depending not only on the type andseverity of the soils and stains, but also on the wash watertemperature, the volume of wash water and the type of washing machine.

In a preferred use aspect a dispensing device is employed in the washingmethod. The dispensing device is charged with the detergent product, andis used to introduce the product directly into the drum of the washingmachine before the commencement of the wash cycle. Its volume capacityshould be such as to be able to contain sufficient detergent product aswould normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensingdevice containing the detergent product is placed inside the drum. Atthe commencement of the wash cycle of the washing machine water isintroduced into the drum and the drum periodically rotates. The designof the dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product duringthe wash cycle in response to its agitation as the drum rotates and alsoas a result of its contact with the wash water.

Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated with awater impermeable protective material so as to retain the contents, suchas is disclosed in European published Patent Application No. 0018678.Alternatively it may be formed of a water-insoluble synthetic polymericmaterial provided with an edge seal or closure designed to rupture inaqueous media as disclosed in European published Patent Application Nos.0011500, 0011501, 0011502, and 0011968. A convenient form of waterfrangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric filmsuch as polyethylene or polypropylene.

Machine Dishwashing Method

Any suitable methods for machine washing or cleaning soiled tableware,particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolved ordispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from 8 g to 60 g of productdissolved or dispersed in a wash solution of volume from 3 to 10 liters,as are typical product dosages and wash solution volumes commonlyemployed in conventional machine dishwashing methods.

Packaging for the Compositions

Commercially marketed executions of the bleaching compositions can bepackaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European Application No.94921505.7.

Form of the Skin Care Compositions

The skin care compositions in accordance with the invention can take avariety of physical forms including powder, gel, tablet, bar, paste,cream and liquid forms. The form can be dependent upon the end use ofthe composition. The skin care composition can also be in a tissue, babywipe, or other similar articles.

Form of the Personal Cleansing Compositions

The personal cleansing compositions in accordance with the invention cantake a variety of physical forms including powder, gel, tablet, bar,paste, cream and liquid forms. The form can be dependent upon the enduse of the composition.

Form of the Fabric Softener Compositions

Solid Particulate Compositions—The invention also comprises solidparticulate composition comprising:

from about 50% to about 95%, preferably from about 60% to about 90%, ofsaid biodegradable fabric softening active;

optionally, from 0% to about 30%, preferably from about 3% to about 15%,of dispersibility modifier; and

from 0% to about 10% of a pH modifier.

Optional pH Modifier

Since the biodegradable ester fabric softener actives are somewhatlabile to hydrolysis, it is preferable to include optional pH modifiersin the solid particulate fabric softener compositions to which water isto be added, to form stable dilute or concentrated liquid softenercompositions. Said stable liquid fabric softener compositions shouldhave a pH (neat) of from about 2 to about 5, preferably from about 2 toabout 4.5, more preferably from about 2 to about 4.

The pH can be adjusted by incorporating a solid, water soluble Bronstedacid. Examples of suitable Bronsted acids include inorganic mineralacids, such as boric acid, sodium bisulfate, potassium bisulfate, sodiumphosphate monobasic, potassium phosphate monobasic, and mixturesthereof, organic acids, such as citric acid, fumaric acid, maleic acid,malic acid, tannic acid, gluconic acid, glutamic acid, tartaric acid,glycolic acid, chloroacetic acid, phenoxyacetic acid, 1,2,3,4-butanetetracarboxylic acid, benzene sulfonic acid, benzene phosphonic acid,ortho-toluene sulfonic acid, para-toluene sulfonic acid, phenol sulfonicacid, naphthalene sulfonic acid, oxalic acid, 1,2,4,5-pyromellitic acid,1,2,4-trimellitic acid, adipic acid, benzoic acid, phenylacetic acid,salicylic acid, succinic acid, and mixtures thereof; and mixtures ofmineral inorganic acids and organic acids. Preferred pH modifiers arecitric acid, gluconic acid, tartaric acid, 1,2,3,4-butanetetracarboxylic acid, malic acid, and mixtures thereof.

Optionally, materials that can form solid clathrates such ascyclodextrins and/or zeolites, etc., can be used as adjuvants in thesolid particulate composition as host carriers of concentrated liquidacids and/or anhydrides, such as acetic acid, HCl, sulfuric acid,phosphoric acid, nitric acid, carbonic acid, etc. An example of suchsolid clathrates is carbon dioxide adsorbed in zeolite A, as disclosedin U.S. Pat. No. 3,888,998, Whyte and Samps, issued Jun. 10, 1975 andU.S. Pat. No. 4,007,134, Liepe and Japikse, issued Feb. 8, 1977, both ofsaid patents being incorporated herein by reference. Examples ofinclusion complexes of phosphoric acid, sulfuric acid, and nitric acid,and process for their preparation are disclosed in U.S. Pat. No.4,365,061, issued Dec. 21, 1982 to Szejtli et al., said patent beingincorporated herein by reference.

When used, the pH modifier is typically used at a level of from about0.01% to about 10%, preferably from about 0.1% to about 5%, by weight ofthe composition.

Preparation of Solid Particulate Granular Fabric Softener

The granules can be formed by preparing a melt, solidifying it bycooling, and then grinding and sieving to the desired size. In athree-component mixture, e.g., nonionic surfactant, single-long-chaincationic, and DEQA, it is more preferred, when forming the granules, topre-mix the nonionic surfactant and the more soluble single-long-chainalkyl cationic compound before mixing in a melt of the diesterquaternary ammonium cationic compound.

It is highly preferred that the primary particles of the granules have adiameter of from about 50 to about 1,000, preferably from about 50 toabout 400, more preferably from about 50 to about 200, microns. Thegranules can comprise smaller and larger particles, but preferably fromabout 85% to about 95%, more preferably from about 95% to about 100%,are within the indicated ranges. Smaller and larger particles do notprovide optimum emulsions/dispersions when added to water. Other methodsof preparing the primary particles can be used including spray coolingof the melt. The primary particles can be agglomerated to form adust-free, non-tacky, free-flowing powder. The agglomeration can takeplace in a conventional agglomeration unit (i.e., Zig-Zag Blender,Lodige) by means of a water-soluble binder. Examples of water-solublebinders useful in the above agglomeration process include glycerol,polyethylene glycols, polymers such as PVA, polyacrylates, and naturalpolymers such as sugars.

The flowability of the granules can be improved by treating the surfaceof the granules with flow improvers such as clay, silica or zeoliteparticles, water-soluble inorganic salts, starch, etc.

Method of Use

Water can be added to the particulate, solid, granular compositions toform dilute or concentrated liquid softener compositions for lateraddition to the rinse cycle of the laundry process with a concentrationof said biodegradable cationic softening compound of from about 0.5% toabout 50%, preferably from about 1% to about 35%, more preferably fromabout 4% to about 32%. The particulate, rinse-added solid composition(1) can also be used directly in the rinse bath to provide adequateusage concentration (e.g., from about 10 to about 1,000 ppm, preferablyfrom about 50 to about 500 ppm, of total softener active ingredient).The liquid compositions can be added to the rinse to provide the sameusage concentrations.

The water temperature for preparation should be from about 20° C. toabout 90° C., preferably from about 25° C. to about 80° C.Single-long-chain alkyl cationic surfactants as theviscosity/dispersibility modifier at a level of from 0% to about 15%,preferably from about 3% to about 15%, more preferably from about 5% toabout 15%, by weight of the composition, are preferred for the solidcomposition. Nonionic surfactants at a level of from about 5% to about20%, preferably from about 8% to about 15%, as well as mixtures of theseagents can also serve effectively as the viscosity/dispersibilitymodifier.

The emulsified/dispersed particles, formed when the said granules areadded to water to form aqueous concentrates, typically have an averageparticle size of less than about 10 microns, preferably less than about2 microns, and more preferably from about 0.2 to about 2 microns, inorder that effective deposition onto fabrics is achieved. The term“average particle size,” in the context of this specification, means anumber average particle size, i.e., more than 50% of the particles havea diameter less than the specified size.

Particle size for the emulsified/dispersed particles is determinedusing, e.g., a Malvern particle size analyzer.

Depending upon the particular selection of nonionic and cationicsurfactant, it may be desirable in certain cases, when using the solidsto prepare the liquid, to employ an efficient means for dispersing andemulsifying the particles (e.g., blender).

Solid particulate compositions used to make liquid compositions can,optionally, contain electrolytes, perfume, antifoam agents, flow aids(e.g., silica), dye, preservatives, and/or other optional ingredientsdescribed hereinbefore.

The benefits of adding water to the particulate solid composition toform aqueous compositions to be added later to the rinse bath includethe ability to transport less weight thereby making shipping moreeconomical, and the ability to form liquid compositions similar to thosethat are normally sold to consumers, e.g., those that are describedherein, with lower energy input (i.e., less shear and/or lowertemperature). Furthermore, the particulate granular solid fabricsoftener compositions, when sold directly to the consumers, have lesspackaging requirements and smaller, more disposable containers. Theconsumers will then add the compositions to available, more permanent,containers, and add water to pre-dilute the compositions, which are thenready for use in the rinse bath, just like the liquid compositionsherein. The liquid form is easier to handle, since it simplifiesmeasuring and dispensing.

Dryer Activated Compositions—The present invention also relates toimproved solid dryer-activated fabric softener compositions which areeither incorporated into articles of manufacture, e.g., on a substrate,or, are in the form of particles similar to those disclosed above.(including, where appropriate, agglomerates, pellets, and tablets ofsaid particles). Such compositions typically contain from about 10% toabout 95% of fabric softening agent.

Substrate Articles—In preferred embodiments, the present inventionencompasses articles of manufacture. Representative articles are thosethat are adapted for use to provide unique perfume benefits and tosoften fabrics in an automatic laundry dryer, of the types disclosed inU.S. Pat. No.: 3,989,631 Marsan, issued Nov. 2, 1976; U.S. Pat. No.4,055,248, Marsan, issued Oct. 25, 1977; U.S. Pat. No. 4,073,996, Bedenket al., issued Feb. 14, 1978; U.S. Pat. No. 4,022,938, Zaki et al.,issued May 10, 1977; U.S. Pat. No. 4,764,289, Trinh, issued Aug. 16,1988; U.S. Pat. No. 4,808,086, Evans et al., issued Feb. 28, 1989; U.S.Pat. No. 4,103,047, Zaki et al., issued Jul. 25, 1978; U.S. Pat. No.3,736,668, Dillarstone, issued Jun. 5, 1973; U.S. Pat. No. 3,701,202,Compa et al., issued Oct. 31,1972; U.S. Pat. No. 3,634,947, Furgal,issued Jan. 18, 1972; U.S. Pat. No. 3,633,538, Hoeflin, issued Jan. 11,1972; and U.S. Pat. No. 3,435,537, Rumsey, issued Apr. 1, 1969; and U.S.Pat. No. 4,000,340, Murphy et al., issued Dec. 28, 1976, all of saidpatents being incorporated herein by reference.

Typical articles of manufacture of this type include articlescomprising:

I. a fabric conditioning composition comprising from about 30% to about95% of normally solid, dryer softenable fabric softening agentcomprising said biodegradable fabric softening active; and

II. a dispensing means which provides for release of an effective amountof said composition including an effective amount of ii, sufficient toprovide odor control, to fabrics in an automatic laundry dryer atautomatic laundry dryer operating temperatures, e.g., from about 35° C.to 115° C.

When the dispensing means is a flexible substrate, e.g., in sheetconfiguration, the fabric conditioning composition is releasably affixedon the substrate to provide a weight ratio of conditioning compositionto dry substrate ranging from about 10:1 to about 0.5:1, preferably fromabout 5:1 to about 1:1.

The solid fabric softener compositions herein can include cationic andnonionic fabric softener actives used in combination with each other.

In the following Examples, the abbreviations for the various ingredientsused for the compositions have the following meanings.

MBFA Mid-chain branched fatty acid MBFS Salt of Mid-chain branched fattyacid MES Alkyl methyl ester sulfonate SAS Secondary alkyl sulfate NaPSSodium paraffin sulfonate C45AS Sodium C₁₄-C₁₅ linear alkyl sulfateCxyAS Sodium C_(1x)-C_(1y) alkyl sulfate (or other salt if specified)CxyEzS Sodium C_(1x)-C_(1y) alkyl sulfate condensed LAS Sodium linearalkyl benzene sulfonate Citric acid Anhydrous citric acid LMFAA C12-14alkyl N-methyl glucamide CxyFA C_(1x)-C_(1y) fatty acid CxyEz AC_(1x-1y) branched primary alcohol condensed with an average of z molesof ethylene oxide Carbonate Anhydrous sodium carbonate with a particlesize between 200 μm and 900 μm Citrate Tri-sodium citrate dihydrate ofactivity 86.4% with a particle size distribution between 425 μm and 850μm TFAA C16-18 alkyl N-methyl glucamide Fatty Acid C12-C14 fatty acid(C12/14) Fatty Acid Topped palm kernel fatty acid (TPK) Fatty AcidRapeseed fatty acid (RPS) Borax Na tetraborate decahydrate PAAPolyacrylic Acid (mw = 4500) PEG Polyethylene glycol (mw = 4600) with zmoles of ethylene oxide (or other salt if specified) CxyEz A C_(1x-1y)branched primary alcohol condensed with an average of z moles ofethylene oxide AQA R₂.N⁺(CH₃)_(x)((C₂H₄O)yH)z with R₂ = C₈-C₁₈ x + z =3, x = 0 to 3, z = 0 to 3, y = 1 to 15. STPP Anhydrous sodiumtripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formulaNa₁₂(A10₂SiO₂)₁₂.27H₂O having a primary particle size in the range from0.1 to 10 micrometers NaSKS-6 Crystalline layered silicate of formulaδ-Na₂Si₂O₅ Carbonate Anhydrous sodium carbonate with a particle sizebetween 200 μm and 900 μm Bicarbonate Anhydrous sodium bicarbonate witha particle size distribution between 400 μm and 1200 μm SilicateAmorphous Sodium Silicate (SiO₂:Na₂O; 2.0 ratio) Sulfate Anhydroussodium sulfate PAE ethoxylated tetraethylene pentamine PIE ethoxylatedpolyethylene imine PAEC methyl quaternized ethoxylated dihexylenetriamine MA/AA Copolymer of 1:4 maleic/acrylic acid, average molecularweight about 70,000. CMC Sodium carboxymethyl cellulose ProteaseProteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S underthe tradename Savinase Cellulase Cellulytic enzyme of activity 1000CEVU/g sold by NOVO Industries A/S under the tradename Carezyme AmylaseAmylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S underthe tradename Termamyl 60T Lipase Lipolytic enzyme of activity 100kLU/gsold by NOVO Industries A/S under the tradename Lipolase PBl Anhydroussodium perborate bleach of nominal formula NaBO₂.H₂O₂ PercarbonateSodium Percarbonate of nominal formula 2Na₂CO₃.3H₂O₂ NaDCC Sodiumdichloroisocyanurate NOBS Nonanoyloxybenzene sulfonate, sodium salt TAEDTetraacetylethylenediamine DTPMP Diethylene triamine penta (methylenephosphonate), marketed by Monsanto under Trade name Dequest 2060Photoactivated Sulfonated Zinc Phthalocyanine bleach encapsulated inbleach dextrin soluble polymer Brightener 1 Disodium4,4′-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium4,4′-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino)stilbene-2:2′-disulfonate. HEDP 1,1-hydroxyethane diphosphonic acid SRP1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloylbackbone SRP 2 sulfonated ethoxylated terephthalate polymer SRP 3 methylcapped ethoxylated terephthalate polymer Silicone Polydimethylsiloxanefoam controller with siloxane- antifoam oxyalkylene copolymer asdispersing agent with a ratio of said foam controller to said dispersingagent of 10:1 to 100:1. DTPA Diethylene triamine pentaacetic acidEndolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVOIndustries A/S MEA Monoethanolamine PG Propanediol BPP Butoxy -propoxy - propanol EtOH Ethanol NaOH Solution of sodium hydroxide NaTSSodium toluene sulfonate TFAA C16-18 alkyl N-methyl glucamide LMFAAC12-14 alkyl N-methyl glucamide APA C8-C10 amido propyl dimethyl amineIsofol 16 Condea trademark for C16 (average) Guerbet alcohols

In the following Examples all levels are quoted as % by weight of thecomposition. The following examples are illustrative of the presentinvention, but are not meant to limit or otherwise define its scope. Allparts, percentages and ratios used herein are expressed as percentweight unless otherwise specified.

EXAMPLE I

The following laundry detergent compositions A to D are prepared inaccord with the invention:

A B C D MBFS¹ 2 4.0 4.0 8.0 C45AS 6 4.0 2.8 — LAS — — 1.2 — C25E3 3.43.4 3.4 3.4 AQA 0.4 0.5 0.6 0.8 Zeolite A 18.1 18.1 18.1 18.1 Carbonate13.0 13.0 13.0 27.0 Silicate 1.4 1.4 1.4 3.0 Sulfate 26.1 26.1 26.1 26.1PBl 9.0 9.0 9.0 9.0 TAED 1.5 1.5. 1.5 1.5 DTPMP 0.25 0.25 0.25 0.25 HEDP0.3 0.3 0.3 0.3 Protease 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1MA/AA 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 Photoactivated bleach 15 ppm15 ppm 15 ppm 15 ppm Brightener 1 0.09 0.09 0.09 0.09 Perfume 0.3 0.30.3 0.3 Silicone antifoam 0.5 0.5 0.5 0.5 Misc/minors to 100% Density ing/liter 850 850 850 850 ¹Mid-branched fatty soaps are selected accordingto the invention as exemplified by Example 78

EXAMPLE II

The following laundry detergent compositions E to I are prepared inaccord with the invention:

E F G H I MBFS¹ 22   16.5  11 1-5.5 10-25 Any Combination of: 0   1-5.511   16.5  0-5 C45 AS C45E1S LAS C16 SAS C14-17 NaPS C14-18 MES AQA0-2   0-2   0-2   0-2   0-4 C23E6.5 or C45E7 1.5 1.5 1.5 1.5 0-4 ZeoliteA 27.8  27.8  27.8  27.8  20-30 PAA 2.3 2.3 2.3 2.3 0-5 Carbonate 27.3 27.3  27.3  27.3  20-30 Silicate 0.6 0.6 0.6 0.6 0-2 PB1 1.0 1.0 1.0 1.00-3 Protease 0-0.5 0-0.5 0-0.5 0-0.5   0-0.5 Cellulase 0-0.3 0-0.3 0-0.30-0.3   0-0.5 Amylase 0-0.5 0-0.5 0-0.5 0-0.5 0-1 SRP 1 0.4 0.4 0.4 0.40-1 Brightener 1 or 2 0.2 0.2 0.2 0.2   0-0.3 PEG 1.6 1.6 1.6 1.6 0-2Sulfate 5.5 5.5 5.5 5.5 0-6 Silicone Antifoam  0.42  0.42  0.42  0.42  0-0.5 Moisture & Minors Balance Density (g/L) 663    663    663   663    600-700 ¹Mid-branched fatty soaps are selected according to theinvention as exemplified by example 78

EXAMPLE III

The following laundry detergent compositions J to N are prepared inaccord with the invention:

J K L M N MBFS¹ 16.5  12.5  8.5 4    1-25 Any Combination of: 0-6 10  14   18.5   0-20 C45 AS C45E1S LAS C16 SAS C14-17 NaPS C14-18 MES AQA0-2 0-2 0-2 0-2 0-4 TFAA 1.6 1.6 1.6 1.6 0-4 C24E3, C23E6.5 5   5   5  5   0-6 Zeolite A 15   15   15   15   10-30 NaSKS-6 11   11   11   11   5-15 Citrate 3   3   3   3   0-8 MA/AA 4.8 4.8 4.8 4.8 0-8 HEDP 0.5 0.50.5 0.5 0-1 Carbonate 8.5 8.5 8.5 8.5  0-15 Percarbonate or PBI 20.7 20.7  20.7  20.7   0-25 TAED 4.8 4.8 4.8 4.8 0-8 Protease 0.9 0.9 0.90.9 0-1 Lipase  0.15  0.15  0.15  0.15   0-0.3 Cellulase  0.26  0.26 0.26  0.26  0-0.5 Amylase  0.36  0.36  0.36  0.36   0-0.5 SRP 1 0.2 0.20.2 0.2   0-0.5 Brightener 1 or 2 0.2 0.2 0.2 0.2   0-0.4 Sulfate 2.32.3 2.3 2.3  0-25 Silicone Antifoam 0.4 0.4 0.4 0-1 Moisture & MinorsBalance Density (g/L) 850    850    850    850    ¹Mid-branched fattysoaps are selected according to the invention as exemplified by example78

EXAMPLE IV

The following laundry detergent compositions O to T are prepared inaccord with the invention:

O P Q R S T MBFS¹ 32   24   16   8   4    1-35 Any Combina- 0   8   16  24   28    0-35 tion of: C45 AS C45E1S LAS C16 SAS C14-17 NaPS C14-18MES C23E6.5 or 3.6 3.6 3.6 3.6 3.6 0-6 C45E7 AQA 0-1 0-1 0-1 0-1 0-1 0-4Zeolite A 9.0 9.0 9.0 9.0 9.0  0-20 PAA or MA/ 7.0 7.0 7.0 7.0 7.0  0-10AA Carbonate 18.4  18.4  18.4  18.4  18.4   5-25 Silicate 11.3  11.3 11.3  11.3  11.3   5-25 PB1 3.9 3.9 3.9 3.9 3.9 1-6 NOBS 4.1 4.1 4.1 4.14.1 0-6 Protease 0.9 0.9 0.9 0.9 0.9   0-1.3 Amylase   0-0.5   0-0.5  0-0.5   0-0.5   0-0.5   0-0.5 Cellulase   0-0.3   0-0.3   0-0.3  0-0.3   0-0.3   0-0.3 SRP1 0.5 0.5 0.5 0.5 0.5 0-1 Brightener 1 0.30.3 0.3 0.3 0.3   0-0.5 or 2 PEG 0.2 0.2 0.2 0.2 0.2   0-0.5 Sulfate 5.15.1 5.1 5.1 5.1  0-10 Silicone Anti- 0.2 0.2 0.2 0.2 0.2   0-0.5 foamMoisture & Balance Minors Density (g/L) 810    810    810    810   810    810    ¹Mid-branched fatty soaps are selected according to theinvention as exemplified by example 78

EXAMPLE V

The following high density detergent formulations U to X, according tothe present invention, are prepared:

U V W X Agglomerate C45AS 11.0 7.0 4 14.0 MBFS¹ 3.0 10.0 17.0 3.0Zeolite A 15.0 12.0 10.0 10.0 Carbonate 4.0 4.0 4.0 8.0 PAA or MA/AA 4.04.0 4.0 2.0 CMC 0.5 0.5 0.5 0.5 DTPMP 0.4 0.4 0.4 0.4 Spray On C23E6.55.0 5.0 5.0 5.0 Perfume 0.5 0.5 0.5 0.5 Dry Adds C45AS 6.0 6.0 3.0 3.0HEDP 0.5 0.5 0.5 0.3 SKS-6 13.0 13.0 13.0 6.0 Citrate 3.0 3.0 3.0 1.0TAED 5.0 5.0 5.0 7.0 Percarbonate 20.0 20.0 20.0 20.0 SRP 1 0.3 0.3 0.30.3 Protease 1.4 1.4 1.4 1.4 Lipase 0.4 0.4 0.4 0.4 Cellulase 0.6 0.60.6 0.6 Amylase 0.6 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 5.0Brightener 1 0.2 0.2 0.2 0.2 Brightener 2 0.2 0.2 0.2 — Balance(Water/Miscellaneous) 100 100 100 100 Density (g/liter) 850 850 850 850¹Mid-branched fatty soaps are selected according to the invention asexemplified by example 78

EXAMPLE VI

The following laundry detergent compositions Y to BB suitable forhand-washing soiled fabrics are prepared in accord with the invention:

Y Z AA BB MBFS¹ 5 10 18 22 LAS 20 10 11 — STPP 15 30 11 28 Carbonate 158 20 15 Silicates 15 10 15 10 Protease 0 0 0.3 0.3 Perborate 0 0 0 10Sodium Chloride 25 15 20 10 Brightener, perfume 0-0.3 0.2 0.2 0.2Moisture & Minors² Balance ¹Mid-branched fatty soaps are selectedaccording to the invention as exemplified by example 78 ²Can be selectedfrom convenient materials such as CaCO₃, talc, clay, sulfates,silicates, and the like.

EXAMPLE VII

The following laundry detergent compositions CC to FF suitable forhand-washing soiled fabrics are prepared in accord with the invention:

CC DD EE FF MBFS¹ 22 16 11  1-6 Any Combination of:  0 0-5 5-15 10-20C45 AS C45E1S C45E3S LAS AQA 0-5 0-1 0-5  0-3 Any Combination of: 0-20-4 0-2  0-2 C23E6.5 C45E7 STPP 5-45 5-45 5-45  5-45 PAA 0-2 0-2 0-2 0-2 CMC 0-0.5 0-0.5 0-0.5  0-0.5 Protease 0-0.5 0-0.5 0-0.5  0-0.5Cellulase 0-0.3 0-0.3 0-0.3  0-0.3 Amylase 0-0.5 0-0.5 0-0.5  0-0.5 SRP0-0.5  0.4 0-0.5  0-0.5 Brightener, perfume 0-0.3 0-0.2 0-0.3  0-00.2Photobleach 0-0.1 0-0.1 0-0.1  0-0.1 Carbonate 15 10 20 15 Silicate  715 10  8 Sulfate  5  5  5  5 Moisture & Minors² ---Balance---¹Mid-branched fatty soaps are selected according to the invention asexemplified by example 78 ²Can be selected from convenient materialssuch as CaCO₃, NaCl, talc, clay, sulfates, silicates, and the like.

EXAMPLE VIII

Light-duty liquid dishwashing detergent compositions comprising themid-chain branched soaps of the present claims are prepared:

Wt. % Wt. % Wt. % Wt. % Ingredient GG HH II JJ C23E0.6S 25 20 15 0 C23E91 1 1 1 MBFS¹ 5 10 15 30 LMFAA 4 4 4 4 Coconut amine oxide 4 4 4 4 EO/POBlock Co-polymer- 0.5 0.5 0.5 0.5 Tetronic ® 704 EtOH 6 6 6 6 Calciumxylene sulfonate 5 5 5 5 Magnesium⁺⁺ (added as chloride) 3.0 3.0 3.0 3.0Water, thickeners and minors to 100% to 100% to 100% to 100% pH @ 10%(as made) 7.5 7.5 7.5 7.5 ¹Mid-branched fatty soaps are selectedaccording to the invention as exemplified by example 78

EXAMPLE IX

This example illustrates the preparation and performance advantages ofthe mid-chain branched fatty acid containing non-aqueous liquiddetergent compositions of the instant invention. Such examples, however,are not necessarily meant to limit or otherwise define the scope of theinvention herein. All parts, percentages and ratios used herein areexpressed as percent weight unless otherwise specified.

Preparation of LAS Powder for Use as a Structurant

Sodium C₁₂ linear alkyl benzene sulfonate (NaLAS) is processed into apowder containing two phases. One of these phases is soluble in thenon-aqueous liquid detergent compositions herein and the other phase isinsoluble. It is the insoluble fraction which serves to add structureand particle suspending capability to the non-aqueous phase of thecompositions herein.

NaLAS powder is produced by taking a slurry of NaLAS in water(approximately 40-50% active) combined with dissolved sodium sulfate(3-15%) and hydrotrope, sodium sulfosuccinate (1-3%). The hydrotrope andsulfate are used to improve the characteristics of the dry powder. Adrum dryer is used to dry the slurry into a flake. When the NaLAS isdried with the sodium sulfate, two distinct phases are created withinthe flake. The insoluble phase creates a network structure of aggregatesmall particles (0.4-2 um) which allows the finished non-aqueousdetergent product to stably suspend solids.

The NaLAS powder prepared according to this example has the followingmakeup shown in Table I.

TABLE I LAS Powder Component Wt. % NaLAS 85% Sulfate 11% Sulfosuccinate2% Water 2.5% Unreacted, etc. balance to 100% % insoluble LAS 17% # ofphase (via X-ray diffraction) 2

TABLE II Non-aqueous based heavy duty liquid laundry detergentcompositions (KK to OO) which comprise the mid-chain branched acids ofthe present invention are presented below. Non-Aqueous Liquid DetergentComposition with Bleach Wt % Wt % Wt % Wt % Wt % Component KK LL MM NNOO LAS, From Above 16 13 8 8 2 MBFA¹ 22 25 28 30 34 BPP 19 19 19 19 19Citrate 3 3 3 3 3 Bleach activator 5.9 5.9 5.9 5.9 5.9 Carbonate 9 9 9 99 MA/AA 3 3 3 3 3 Colored speckles 0.4 0.4 0.4 0.4 0.4 EDDS 1 1 1 1 1Cellulase Prills 0.1 0.1 0.1 0.1 0.1 Amylase Prills 0.4 0.4 0.4 0.4 0.4Ethoxylated diamine quat 1.3 1.3 1.3 1.3 1.3 Perborate 15 15 15 15 15Optionals including: balance balance balance balance balance brightener,colorant, perfume, thickener, suds suppressor, colored speckles etc.100% 100% 100% 100% 100% ¹Mid-branched fatty acids are selectedaccording to the invention as exemplified by any of examples 1-78 ormixtures thereof.

The resulting Table II composition is a stable, anhydrous heavy-dutyliquid laundry detergent which provides excellent stain and soil removalperformance when used in normal fabric laundering operations.

EXAMPLE X

Aqueous based heavy duty liquid laundry detergent compositions PP to TTwhich comprise the mid-chain branched soaps of the present invention arepresented below.

Ingredient PP QQ RR SS TT MBFS 10 8 6 4 2 Na C25AE1.8S 10 12 14 16 18C23E9 2 2 2 2 2 LMFAA 5 5 5 5 0 Citric acid builder 3 3 3 3 3 Fatty acidbuilder 0 1 2 4 5 PAE 1 1 1.2 1.2 0.5 PG 8 8 8 8 4.5 EtOH 4 4 4 4 2Boric acid 3.5 3.5 3.5 3.5 2 Sodium Cumene 3 3 3 3 0 Sulfonate pH = 8.08.0 8.0 8.0 7.0 Enzymes, dyes, water balance balance balance balancebalance 100% 100% 100% 100% 100% ¹Mid-branched fatty soaps are selectedaccording to the invention as exemplified by example 78

EXAMPLE XI

The following aqueous liquid laundry detergent compositions UU to YY areprepared in accord with the invention:

UU VV WW XX YY MBFS 1-7  7-12 12-17 17-22  1-35 Any combination of:15-21 10-15  5-10 0-5  0-25 C25 AExS * Na (x = 1.8 − 2.5) C25 AS (linearto high 2-alkyl) C14-17 NaPS C12-16 SAS C18 1,4 disulfate LAS C12-16 MESLMFAA   0-3.5   0-3.5   0-3.5   0-3.5 0-8 C23E9 or C23E6.5 0-2 0-2 0-20-2 0-8 APA 0.5 0.5 0.5 0.5 0.5-2   Citric Acid 5 5 3 3 0-8 Fatty Acid(TPK or 4 3 2 1  0-14 C12/14) EtOH 4 4 4 4 0-8 PG 6 6 6 6  0-10 MEA 1 11 1 0-3 NaOH 3 3 3 3 0-7 Na TS 2.3 2.3 2.3 2.3 0-4 Na formate 0.1 0.10.1 0.1 0-1 Borax 2.5 2.5 2.5 2.5 0-5 Protease 0.9 0.9 0.9 0.9   0-1.3Lipase 0.06 0.06 0.06 0.06   0-0.3 Amylase 0.15 0.15 0.15 0.15   0-0.4Cellulase 0.05 0.05 0.05 0.05   0-0.2 PAE   0-0.6   0-0.6   0-0.6  0-0.6   0-2.5 PIE 1.2 1.2 1.2 1.2   0-2.5 PAEC   0-0.4   0-0.4   0-0.4  0-0.4 0-2 SRP 2 0.2 0.2 0.2 0.2   0-0.5 Brightener 1 or 2 0.15 0.150.15 0.15   0-0.5 Silicone antifoam 0.12 0.12 0.12 0.12   0-0.3 FumedSilica 0.0015 0.0015 0.0015 0.0015    0-0.003 Perfume 0.3 0.3 0.3 0.3  0-0.6 Dye 0.0013 0.0013 0.0013 0.0013    0-0.003 Moisture/minorsBalance Balance Balance Balance Balance Product pH (10% in 7.7 7.7 7.77.7   6-9.5 DI water) ¹Mid-branched fatty soaps are selected accordingto the invention as exemplified by example 78

EXAMPLE XII Clear Fabric Softener Compositions With Various FabricSoftener Levels and Solvent Systems

Component (Wt %) A1 B1 C1 D1 E1 F1 G1 H1 I1 TEA 30 35 30 30 30 35 30 3530 Diester Quat¹ Ethanol 2.47 2.88 2.47 2.47 2.47 2.88 2.47 2.88 2.47(from active) Hexylene 2.7 3.1 2.7 2.7 2.7 3.1 2.7 3.1 2.7 Glycol (fromactive) TMPD 4 5 — 5 5 — — — 5.5 Hexylene — — 6 — — 10 — 2 — Glycol2-Ethyl- — — — — — — 6 — — 1,3-Hexane-diol Neodol 5 6 4 6 6 5 5 5 6 91-8Pluronic 1 1 1 1 1 1 1 1 1 L-35O HCl 0-0.25 0-0.25 0-0.25 0-0.25 0-0.250-0.25 0-0.25 0-0.25 0-0.25 MgCl2 1.75 1.75 2.00 1.75 1.75 2.20 1.501.75 1.75 Perfume 2.2 2.5 2.5 2 2.5 3 2 2 2 DTPA 0.01 0.01 0.01 0.010.01 0.01 0.01 0.01 0.01 Blue Dye 0.0003 0.0003 0.0003 0.0003 0.00030.0003 0.0003 0.0003 0.0003 Deionized Bal. Bal. Bal. Bal. Bal. Bal. Bal.Bal. Bal. Water & Minors ¹Di(acyloxyethyl)(2-hydroxyethyl)methylammonium methyl sulfate where the acyl group is derived from a mixtureof partially hydrogenated canola fatty acid and the branched acid ofexample 1.

EXAMPLE XIII Clear Fabric Softener Compositions With Low Solvent Levelsand Various Principal Solvents

Component Wt % J1 K1 L1 M1 N1 O1 TEA Di-ester Quat¹. 30 30 45 40 45 30Ethanol from 2.47 2.47 3.71 3.29 3.71 2.47 softener active HexyleneGlycol 2.65 2.65 3.97 3.53 3.97 2.65 from softener active PrincipalSolvent: TMPD 5 5 — — — 4 1,2-Hexanediol — — 1 — — — 1,2-Pentanediol — —— 1 — — 1,2-Butanediol — — — — 3 — Phase Stabilizer: Neodol 91-8 5 5 — —— 5 Rewopal C6 — — 2.9 2.9 2.9 — Pluronic L35 1 1 0.5 1 — 1 MgCl2 1.75 —— — — 1.75 CaCl2 — 1.75 — — — — Perfume 1.8 2.0 1.5 1.5 1.5 2.2De-ionized Water & Bal. Bal. Bal. Bal. Bal. Bal. minors¹Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate wherethe acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid and the branched acid of example 2.

Clear Fabric Softening Compositions with 45% Fabric Softener Active andVarious Electrolytes and Solvent Systems.

Com- ponent Wt % P1 Q1 R1 S1 T1 U1 V1 W1 TBA 45 45 45 45 45 45 45 45Di-ester Quat.¹ Ethanol 7 — 3.71 3.71 3.71 3.71 3.71 3.71 (from active)Hexy- — 3.97 3.97 3.97 3.97 3.97 3.97 3.97 lene Glycol (from active)Hexy- — 2.03 — — — — — — lene Glycol Pinacol — — 3 — — — — — Neo- — — —3 — — — — pentyl Glycol Isopro- — — — — — — 3 — panol Butyl — — — — — —— 3.1 Carbitol 1,5- — — — — — 3 — — Hex- anediol Rewo- 3 3 3 3 3 3 3 3.6pal C6 Electro- KCl CaCl2 KCl CaCl2 K Ci- K Ci- CaCl2 Ca- lyte tratetrate Cl2 % of 1 1 1 1 2 2 1 1.2 Electro- lyte Perfume 1.5 1.5 1.5 1.51.5 1.5 1.5 2 De- Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. ionized Water¹Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate wherethe acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid, the branched acid of example 1 and the branched acidof example 3.

Clear Fabric Softening Compositions with Hexylene Glycol as PrincipalSolvent.

Component Wt % X1 Y1 Z1 A2 B2 C2 D2 E2 F2 G2 H2 TBA Di- 45 45 45 45 4530 28 32 32 36 36 ester Quat.¹ Ethanol 3.7 3.7 3.7 3.7 3.7 2.5 2.3 2.62.6 3.3 3.3 (from active) Hexylene Glycol 4 4 4 4 4 2.7 2.5 2.8 2.8 — —(from active) Hexylene Glycol 3 6 9 7.3 3 9 3 3.3 6.1 6.5 6.5 Rewopal C63.5 2.5 1.5 3.1 2.9 3 — — — 1.8 1.8 Neodol 91-8 — — — — — — 3.1 3.0 4.9— — CaCl2 1.1 1.1 0.8 2 1 0.95 2.1 2 1 — 1.2 Sodium — — — — — — — — — 1— Cumene Sulfonate Perfume 2.0 2.0 2.0 2.0 1.5 1.5 1.0 1.1 3.2 1.2 1.2De-ionized Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Water¹Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate wherethe acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid and a mixture of the branched acids of examples 6, 9and 11-13.

EXAMPLE XIV Dispersion Examples

The compositions of Example XIV are made at ambient temperature by thefollowing process:

1. Prepare the water seat containing HCl.

2. Separately, mix perfume and Tenox antioxidant to the diester softeneractive.

3. Add the diester active blend into the water seat with mixing.

4. Add about 10-20% of the CaCl₂ solution at approximately halfwaythrough the diester addition.

5. Add the remainder of the CaCl₂ solution after the diester addition iscomplete with mixing.

Ingredients Wt. % I2 J2 K2 L2 M2 N2 DEQA2 (85% 18 — 15 — — — active inethanol) DEQA8 (85% — 18 — 12 — — active in ethanol) DEQA10 9.2 9.2 1512 — — (85% active in ethanol) DEQA24 — — — — — 20.8 (85% active inethanol) DEQA25 — — — — — 28 (85% active in ethanol) Perfume 1.35 1.351.35 1.35 1.35 1.35 Tenox 6 0.04 0.04 0.04 0.04 0.04 0.04 CaCl2 (25% 2 22 2 2 2 solution) HCl 1N 0.30 0.30 0.30 0.30 0.30 0.30 Distilled Bal.Bal. Bal. Bal. Bal. Bal. Water

DEQA2 is Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewhere the acyl group is derived from a partially hydrogenated canolafatty acid 85% active.

DEQA8 is Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewhere the acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid and a mixture of the branched acids of examples 16-23,85% active.

DEQA10 is Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewhere the acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid and a mixture of the branched acids of examples 24 to30, 85% active.

DEQA24 is Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewhere the acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid and the branched acid of example 13, 85% active.

DEQA25 is Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewhere the acyl group is derived from a mixture of partially hydrogenatedcanola fatty acid and a mixture of the branched acids of examples 30-35,38-42, 62-65 and 73, 85% active.

The above Examples show dispersion compositions with good stability andperformance.

What is claimed is:
 1. A composition of matter comprising branchedcarboxylic acids having 19 carbon atoms in total chain length, and thelower alkyl esters, the stereoisomers, or the salts thereof, whereinsaid composition of matter comprises: (a) at least one branchedcarboxylic acid selected from the group comprising 2,3-, 2,7-, 2,8-,2,9-, 2,11-, 2,12-, 2,13-, 2,15- and 2,16-dimethylheptadecanoic acid;and mixtures thereof; (b) at least one branched carboxylic acid selectedfrom the group comprising 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,10-, 3,12-,3,13-, 3,14-, 3,15-, 3,16-, 4,5-, 4,7-, 4,9-, 4,11-, 4,13-, 4,15-,4,16-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-, 5,12-, 5,13-, 5,14-, 5,15-,5,16-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-, 6,13-, 6,15-, 6,16-, 7,8-,7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-, 7,15-, 7,16-, 8,9-, 8,11-,8,12-, 8,13-, 8,15-, 8,16-, 9,10-, 9,11-, 9,12-, 9,13-, 9,14-, 9,15-,9,16-, 10,11-, 10,12-, 10,13-, 10,15-, 10,16-, 11,12-, 11,13-, 11,14-,11,15-, 11,16-, 12,13-, 12,14-, 12,15-, 13,14-, 13,15-, 13,16-, 14,15-,14,16-, 15,16-, dimethylheptadecanoic acid; and mixtures thereof; and(h) at least one branched carboxylic acid selected from the groupcomprising 2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-,2,3,12-, 2,3,13-, 2,3,14-, 2,3,15-, 2,4,5-, 2,4,6-, 2,4,7-, 2,479-,2,4,10-, 2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-, 2,4,15-, 2,5,6-, 2,5,7-,2,5,8-, 2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,5,13-, 2,5,14-, 2,5,15-,2,6,7-, 2,6,9-, 2,6,11-, 2,6,12-, 2,6,13-, 2,6,14-, 2,6,15-, 2,7,8-,2,7,9-, 2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-, 2,7,15-, 2,8,9-,2,8,11-, 2,8,12-, 2,8,13-, 2,8,14-, 2,8,15-, 2,9,10-, 2,9,11-, 2,9,12-,2,9,13-, 2,9,14-, 2,9,15-, 2,10,11-, 2,10,13-, 2,10,14-, 2,10,15-,2,11,12-, 2,11,13-, 2,11,14-, 2,11,15-, 2,12,13-, 2,12,14-, 2,12,15-,2,13,14-, 2,13,15-, 2,14,15-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-,3,4,10-, 3,4,11-, 3,4,12-, 3,4,13-, 3,4,14-, 3,4,15-, 3,5,6-, 3,5,7-,3,5,8-, 3,5,9-, 3,5,10-, 3,5,11-, 3,5,12-, 3,5,13-, 3,5,14-, 3,5,15-,3,6,7-, 3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,6,13-, 3,6,14-,3,6,15-, 3,7,8-, 3,7,9-, 3,7,10-, 3,7,11-, 3,7,12-, 3,7,13-, 3,7,14-,3,7,15-, 3,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,8,13-, 3,8,14-, 3,8,15-,3,9,10-, 3,9,11-, 3,9,12-, 3,9,13-, 3,9,14-, 3,9,15-, 3,10,11-,3,10,12-, 3,10,13-, 3,10,14-, 3,10,15-, 3,11,12-, 3,11,13-, 3,11,14-,3,11,15-, 3,12,13-, 3,12,14-, 3,12,15-, 3,13,14-, 3,13,15-, 3,14,15-,4,5,6-, 4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,5,13-,4,5,14-, 4,5,15-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-, 4,6,12-,4,6,13-, 4,6,14-, 4,6,15-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,7,12-,4,7,13-, 4,7,14-, 4,7,15-, 4,8,9-, 4,8,10-, 4,8,11-, 4,8,13-, 4,8,15-,4,9,10-, 4,9,11-, 4,9,12-, 4,9,13-, 4,9,14-, 4,9,15-, 4,10,11-,4,10,12-, 4,10,13-, 4,10,14-, 4,10,15-, 4,11,12-, 4,11,13-, 4,11,14-,4,11,15-, 4,12,13-, 4,12,15-, 4,13,14-, 4,13,15-, 4,14,15-, 5,6,7-,5,6,8-, 5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-, 5,6,13-, 5,6,14-, 5,6,15-,5,7,8-, 5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-, 5,7,14-, 5,7,15-,5,8,9-, 5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-, 5,8,14-, 5,8,15-, 5,9,10-,5,9,11-, 5,9,12-, 5,9,13-, 5,9,14-, 5,9,15-, 5,10,11-, 5,10,12-,5,10,13-, 5,10,14-, 5,10,15-, 5,11,12-, 5,11,13-, 5,11,14-, 5,11,15-,5,12,13-, 5,12,14-, 5,12,15-, 5,13,14-, 5,13,15-, 5,14,15-, 6,7,8-,6,7,9-, 6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-, 6,7,15-, 6,8,9-,6,8,10-, 6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,8,15-, 6,9,10-, 6,9,11-,6,9,12-, 6,9,13-, 6,9,14-, 6,9,15-, 6,10,11-, 6,10,13-, 6,10,14-,6,10,15-, 6,11,12-, 6,11,13-, 6,11,14-, 6,11,15-, 6,12,13-, 6,12,14-,6,12,15-, 6,13,14-, 6,13,15-, 6,14,15-, 7,8,9-, 7,8,10-, 7,8,11-,7,8,12-, 7,8,13-, 7,8,14-, 7,8,15-, 7,9,10-, 7,9,11-, 7,9,12-, 7,9,13-,7,9,14-, 7,9,15-, 7,10,11-, 7,10,12-, 7,10,13-, 7,10,14-, 7,10,15-,7,11,12-, 7,11,13-, 7,11,14-, 7,11,15-, 7,12,13-, 7,12,14-, 7,12,15-,7,13,14-, 7,13,15-, 7,14,15-, 8,9,10-, 8,9,11-, 8,9,12-, 8,9,13-,8,9,14-, 8,9,15-, 8,10,11-, 8,10,13-, 8,10,14-, 8,10,15-, 8,11,12-,8,11,13-, 8,11,14-, 8,11,15-, 8,12,13-, 8,12,14-, 8,12,15-, 8,13,14-,8,13,15-, 8,14,15-, 9,10,11-, 9,10,12-, 9,10,13-, 9,10,14-, 9,10,15-,9,11,12-, 9,11,13-, 9,11,14-, 9,11,15-, 9,12,13-, 9,12,14-, 9,12,15-,9,13,14-, 9,13,15-, 9,14,15-, 10,11,12-, 10,11,13-, 10,11,14-,10,11,15-, 10,12,13-, 10,12,14-, 10,12,15-, 10,13,14-, 10,13,15-,10,14,15-, 11,12,13-, 11,12,14-, 11,12,15-, 11,13,14-, 11,13,15-,11,14,15-, 12,13,14-, 12,13,15-, 12,14,15- and13,14,15-trimethylhexadecanoic acid; and mixtures thereof.
 2. Acomposition of matter comprising branched carboxylic acids having 19carbon atoms in total chain length, and the lower alkyl esters, thestereoisomers, or the salts thereof, wherein said composition of mattercomprises: (a) at least one of branched carboxylic acid selected fromthe group comprising 2,3-, 2,7-, 2,8-, 2,9-, 2,11-, 2,12-, 2,13-, 2,15-and 2,16-dimethylheptadecanoic acid; and mixtures thereof; (c) at leastone branched carboxylic acid selected from the group comprising 3-, 4-,5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- and 15-methyl-2-ethylhexadecanoicacid; and mixtures thereof; (f) at least one branched carboxylic acidselected from the group comprising 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-,3,10-, 3,11-, 3,12-, 3,13-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-,4,13-, 5,6-, 5,7-, 5,8-, 5,9-, 5,10-, 5,11-, 5,12-, 5,13-, 6,7-, 6,9-,6,11-, 6,12-, 6,13-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 8,9-,8,10-, 8,11-, 8,12-, 8,13-, 9,10-, 9,11-, 9,12-, 9,13-, 10,11-, 10,12-,10,13-, 11,12-, 11,13- and 12,13-dimethyl-2-ethylpentadecanoic acid; andmixtures thereof; and (g) at least on branched carboxylic acid selectedfrom the group comprising 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-and 14-methyl-2-propylpentadecanoic acid; and mixtures thereof.
 3. Acomposition of matter comprising branched carboxylic acids having 19carbon atoms in total chain length, and the lower alkyl esters, thestereoisomers, or the salts thereof, wherein said composition of mattercomprises: (a) at least one branched carboxylic acid selected from thegroup comprising 2,3-, 2,7-, 2,8-, 2,9-, 2,11-, 2,12-, 2,13-, 2,15- and2,16-dimethylheptadecanoic acid; and mixtures thereof; (b) at least onebranched carboxylic acid selected from the group comprising 3,4-, 3,5-,3,6-, 3,7-, 3,8-, 3,10-, 3,12-, 3,13-, 3,14-, 3,15-, 3,16-, 4,5-, 4,7-,4,9-, 4,11-, 4,13-, 4,15-, 4,16-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-, 5,12-,5,13-, 5,14-, 5,15-, 5,16-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-,6,13-, 6,15-, 6,16-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-,7,15-, 7,16-, 8,9-, 8,11-, 8,12-, 8,13-, 8,15-, 8,16-, 9,10-, 9,11-,9,12-, 9,13-, 9,14-, 9,15-, 9,16-, 10,11-, 10,12-, 10,13-, 10,15-,10,16-, 11,12-, 11,13-, 11,14-, 11,15-, 11,16-, 12,13-, 12,14-, 12,15-,13,14-, 13,15-, 13,16-, 14,15-, 14,16-, 15,16-, dimethylheptadecanoicacid; and mixtures thereof; (c) at least one branched carboxylic acidselected from the group comprising 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12-, 13- and 15-methyl-2-ethylhexadecanoic acid; and mixtures thereof;(f) at least one branched carboxylic acid selected from the groupcomprising 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-,3,13-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 5,6-, 5,7-,5,8-, 5,9-, 5,10-, 5,11-, 5,12-, 5,13-, 6,7-, 6,9-, 6,11-, 6,12-, 6,13-,7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 8,9-, 8,1-, 8,11-, 8,12-, 8,13-,9,10-, 9,11-, 9,12-, 9,13-, 10,11-, 10,12-, 10,13-, 11,12-, 11,13- and12,13-dimethyl-2-ethylpentadecanoic acid; and mixtures thereof; and (g)at least on branched carboxylic acid selected from the group comprising3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- and14-methyl-2-propylpentadecanoic acid; and mixtures thereof.
 4. Acomposition of matter comprising branched carboxylic acids having 19carbon atoms in total chain length, and the lower alkyl esters, thestereoisomers, or the salts thereof, wherein said composition of mattercomprises: (a) at least one branched carboxylic acid selected from thegroup comprising 2,3-, 2,7-, 2,8-, 2,9-, 2,11-, 2,12-, 2,13-, 2,15- and2,16-dimethylheptadecanoic acid; and mixtures thereof; (b) at least onebranched carboxylic acid selected from the group comprising 3,4-, 3,5-,3,6-, 3,7-, 3,8-, 3,10-, 3,12-, 3,13-, 3,14-, 3,15-, 3,16-, 4,5-, 4,7-,4,9-, 4,11-, 4,13-, 4,15-, 4,16-, 5,6-, 5,7-, 5,8-, 5,10-, 5,11-, 5,12-,5,13-, 5,14-, 5,15-, 5,16-, 6,7-, 6,8-, 6,9-, 6,10-, 6,11-, 6,12-,6,13-, 6,15-, 6,16-, 7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 7,14-,7,15-, 7,16-, 8,9-, 8,11-, 8,12-, 8,13-, 8,15-, 8,16-, 9,10-, 9,11-,9,12-, 9,13-, 9,14-, 9,15-, 9,16-, 10,11-, 10,12-, 10,13-, 10,15-,10,16-, 11,12-, 11,13-, 11,14-, 11,15-, 11,16-, 12,13-, 12,14-, 12,15-,13,14-, 13,15-, 13,16-, 14,15-, 14,16-, 15,16-, dimethytheptadecanoicacid; and mixtures thereof; (c) at least one branched carboxylic acidselected from the group comprising 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,12-, 13- and 15-methyl-2-ethylhexadecanoic acid; and mixtures thereof;(f) at least one branched carboxylic acid selected from the groupcomprising 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, 3,9-, 3,10-, 3,11-, 3,12-,3,13-, 4,5-, 4,6-, 4,7-, 4,9-, 4,10-, 4,11-, 4,12-, 4,13-, 5,6-, 5,7-,5,8-, 5,9-, 5,10-, 5,11-, 5,12-, 5,13-, 6,7-, 6,9-, 6,11-, 6,12-, 6,13-,7,8-, 7,9-, 7,10-, 7,11-, 7,12-, 7,13-, 8,9-, 8,10-, 8,11-, 8,12-,8,13-, 9,10-, 9,11-, 9,12-, 9,13-, 10,11-, 10,12-, 10,13-, 11,1,2-,11,13- and 12,13-dimethyl-2-ethylpentadecanoic acid; and mixturesthereof; (g) at least on branched carboxylic acid selected from thegroup comprising 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13- and14-methyl-2-propylpentadecanoic acid; and mixtures thereof; and (h) atleast one branched carboxylic acid selected from the group comprising2,3,5-, 2,3,6-, 2,3,7-, 2,3,8-, 2,3,9-, 2,3,10-, 2,3,11-, 2,3,12-,2,3,13-, 2,3,14-, 2,3,15-, 2,4,5-, 2,4,6-, 2,4,7-, 2,4,9-, 2,4,10-,2,4,11-, 2,4,12-, 2,4,13-, 2,4,14-, 2,4,15-, 2,5,6-, 2,5,7-, 2,5,8-,2,5,9-, 2,5,10-, 2,5,11-, 2,5,12-, 2,5,13-, 2,5,14-, 2,5,15-, 2,6,7-,2,6,9-, 2,6,11-, 2,6,12-, 2,6,13-, 2,6,14-, 2,6,15-, 2,7,8-, 2,7,9-,2,7,10-, 2,7,11-, 2,7,12-, 2,7,13-, 2,7,14-, 2,7,15-, 2,8,9-, 2,8,11-,2,8,12-, 2,8,13-, 2,8,14-, 2,8,15-, 2,9,10-, 2,9,11-, 2,9,12-, 2,9,13-,2,9,14-, 2,9,15-, 2,10,11-, 2,10,13-, 2,10,14-, 2,10,15-, 2,11,12-,2,11,13-, 2,11,14-, 2,11,15-, 2,12,13-, 2,12,14-, 2,12,15-, 2,13,14-,2,13,15-, 2,14,15-, 3,4,5-, 3,4,6-, 3,4,7-, 3,4,8-, 3,4,9-, 3,4,10-,3,4,11-, 3,4,12-, 3,4,13-, 3,4,14-, 3,4,15-, 3,5,6-, 3,5,7-, 3,5,8-,3,5,9-, 3,5,10-, 3,5,11-, 3,5,12-, 3,5,13-, 3,5,14-, 3,5,15-, 3,6,7-,3,6,8-, 3,6,9-, 3,6,10-, 3,6,11-, 3,6,12-, 3,6,13-, 3,6,14-, 3,6,15-,3,7,8-, 3,7,9-, 3,7,10-, 3,7,11-, 3,7,12-, 3,7,13-, 3,7,14-, 3,7,15-,13,8,9-, 3,8,10-, 3,8,11-, 3,8,12-, 3,8,13-, 3,8,14-, 3,8,15-, 3,9,10-,3,9,11-, 3,9,12-, 3,9,13-, 3,9,14-, 3,9,15-, 3,10,11-, 3,10,12-,3,10,13-, 3,10,14-, 3,10,15-, 3,11,12-, 3,11,13-, 3,11,14-, 3,11,15-,3,12,13-, 3,12,14-, 3,12,15-, 3,13,14-, 3,13,15-, 3,14,15-, 4,5,6-,4,5,7-, 4,5,8-, 4,5,9-, 4,5,10-, 4,5,11-, 4,5,12-, 4,5,13-, 4,5,14-,4,5,15-, 4,6,7-, 4,6,8-, 4,6,9-, 4,6,10-, 4,6,11-, 4,6,12-, 4,6,13-,4,6,14-, 4,6,15-, 4,7,8-, 4,7,9-, 4,7,10-, 4,7,11-, 4,7,12-, 4,7,13-,4,7,14-, 4,7,15-, 4,8,9-, 4,8,10-, 4,8,11-, 4,8,13-, 4,8,15-, 4,9,10-,4,9,11-, 4,9,12-, 4,9,13-, 4,9,14-, 4,9,15-, 4,10,11-, 4,10,12-,4,10,13-, 4,10,14-, 4,10,15-, 4,11,12-, 4,11,13-, 4,11,14-, 4,11,15-,4,12,13-, 4,12,15-, 4,13,14-, 4,13,15-, 4,14,15-, 5,6,7-, 5,6,8-,5,6,9-, 5,6,10-, 5,6,11-, 5,6,12-, 5,6,13-, 5,6,14-, 5,6,15-, 5,7,8-,5,7,9-, 5,7,10-, 5,7,11-, 5,7,12-, 5,7,13-, 5,7,14-, 5,7,15-, 5,8,9-,5,8,10-, 5,8,11-, 5,8,12-, 5,8,13-, 5,8,14-, 5,8,15-, 5,9,10-, 5,9,11-,5,9,12-, 5,9,13-, 5,9,14-, 5,9,15-, 5,10,11-, 5,10,12-, 5,10,13-,5,10,14-, 5,10,15-, 5,11,12-, 5,11,13-, 5,11,14-, 5,11,15-, 5,12,13-,5,12,14-, 5,12,15-, 5,13,14-, 5,13,15-, 5,14,15-, 6,7,8-, 6,7,9-,6,7,10-, 6,7,11-, 6,7,12-, 6,7,13-, 6,7,14-, 6,7,15-, 6,8,9-, 6,8,10-,6,8,11-, 6,8,12-, 6,8,13-, 6,8,14-, 6,8,15-, 6,9,10-, 6,9,11-, 6,9,12-,6,9,13-, 6,9,14-, 6,9,15-, 6,10,11-, 6,10,13-, 6,10,14-, 6,10,15-,6,11,12-, 6,11,13-, 6,11,14-, 6,11,15-, 6,12,13-, 6,12,14-, 6,12,15-,6,13,14-, 6,13,15-, 6,14,15-, 7,8,9-, 7,8,10-, 7,8,11-, 7,8,12-,7,8,13-, 7,8,14-, 7,8,15-, 7,9,10-, 7,9,11-, 7,9,12-, 7,9,13-, 7,9,14-,7,9,15-, 7,10,11-, 7,10,12-, 7,10,13-, 7,10,14-, 7,10,15-, 7,11,12-,7,11,13-, 7,11,14-, 7,11,15-, 7,12,13-, 7,12,14-, 7,12,15-, 7,13,14-,7,13,15-, 7,14,15-, 8,9,10-, 8,9,11-, 8,9,12-, 8,9,13-, 8,9,14-,8,9,15-, 8,10,11-, 8,10,13-, 8,10,14-, 8,10,15-, 8,11,12-, 8,11,13-,8,11,14-, 8,11,15-, 8,12,13-, 8,12,14-, 8,12,15-, 8,13,14-, 8,13,15-,8,14,15-, 9,10,11-, 9,10,12-, 9,10,13-, 9,10,14-, 9,10,15-, 9,11,12-,9,11,13-, 9,11,14-, 9,11,15-, 9,12,13-, 9,12,14-, 9,12,15-, 9,13,14-,9,13,15-, 9,14,15-, 10,11,12-, 10,11,13-, 10,11,14-, 10,11,15-,10,12,13-, 10,12,14-, 10,12,15-, 10,13,14-, 10,13,15-, 10,14,15-,11,12,13-, 11,12,14-, 11,12,15-, 11,13,14-, 11,13,15-, 11,14,15-,12,13,14-, 12,13,15-, 12,14,15- and 13,14,15-trimethylhexadecanoic acid,and mixtures thereof.
 5. A composition according to any of claims 1, 2,3, or 4, wherein said composition of matter further comprises a branchedcarboxylic acid selected from the group comprising 3-, 4-, 5-, 6-, 7-,8-, 9-, 10-, 11-, 12-, 13- and 14-ethylheptadecanoic acid; and mixturesthereof.
 6. A composition according to any of claims 1, 2, 3, or 4,wherein said composition of matter further comprises a branchedcarboxylic acid selected from the group comprising 5-, 6-, 7-, 8-, 9-,10-, 11-, 12- and 13-propylhexadecanoic acid; and mixtures thereof.
 7. Acomposition according to any of claims 1, 2, 3, or 4, wherein saidcomposition of matter is substantially free from quatemary-carboncontaining branched carboxylic acid or their salts or derivatives.
 8. Acleaning composition comprising: (i) from about 0.05% to about 99.9%, byweight of a composition of matter according to any of claims 1, 2, 3, or4; and (ii) from about 0.0001 to about 99.99%, by weight of conventionalcleaning additive.
 9. A skin care composition comprising: (i) from about0.05% to about, 99.9%, by weight of a composition of matter according toany of claims 1, 2, 3, or 4; and (ii) from about 0.0001 to about 99.99%,by weight of a conventional skin care additive.
 10. A personal cleansingcomposition comprising: (i) from about 0.05% to about 99.9%, by weightof a composition of matter according to any of claims 1, 2, 3, or 4; and(ii) from about 0.0001 to about 99.99%, by weight of a conventionalpersonal cleansing additive.
 11. A paper article comprising at leastabout 0.001% by weight of said composition of matter according to any ofclaims 1, 2, 3, or
 4. 12. A composition according to any of claims 1, 2,3, or 4, comprising no more than about 0.1% aldehyde impurity.
 13. Acomposition according to any of claims 1, 2, 3, or 4, comprising no morethan about 0.1% unsaturated impurity.
 14. A composition according to anyof claims 1, 2, 3, or 4, comprising at least six of said branchedcarboxylic acids.
 15. A composition according to any of claims 1, 2, 3,or 4, comprising at least 20 of said branched carboxylic acids.